Disulfide stabilized dvd-ig molecules

ABSTRACT

A re-epoxidized polyfunctional epoxy resin composition comprising the reaction product of: (I) an epoxidized polyfunctional epoxy resin oligomeric composition comprising a polyfunctional aliphatic or cycloaliphatic epoxy resin which has been isolated from an epoxy resin product formed as a result of an epoxidation process comprising the reaction of: (i) an aliphatic or cycloaliphatic hydroxyl-containing material; (ii) an epihalohydrin, (iii) a basic-acting substance, in the presence of (iv) a non-Lewis acid catalyst; and (v) optionally, one or more solvents; (II) an epihalohydrin; (III) a basic acting substance; in the presence of (IV) a non-Lewis acid catalyst; and (V) optionally, one or more solvents. A curable epoxy resin composition of the re-epoxidized polyfunctional epoxy resin composition and a thermoset of the curable composition is also disclosed.

This application is a non-provisional application claiming priority fromthe U.S. Provisional Patent Application No. 61/388,064, filed on Sep.30, 2010, entitled “EPOXY RESIN COMPOSITIONS” the teachings of which areincorporated by reference herein, as if reproduced in full hereinbelow.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is related an epoxy resin composition prepared byre-epoxidizing a polyfunctional aliphatic and/or cycloaliphatic epoxyresin precursor derived from an oligomer fraction of an epoxy resin ofan aliphatic and/or cycloaliphatic hydroxyl-containing material. Thepresent invention is additionally related to thermosettable compositionsmade from re-epoxidized polyfunctional aliphatic and/or cycloaliphaticepoxy resins and to thermosets made from said thermosettablecompositions.

2. Description of Background and Related Art

Epoxidation of aliphatic and cycloaliphatic alcohols is an area of longstanding interest, for example as described in EP 0 121 260,incorporated herein by reference. Disclosed in EP 0 121 260 are examplesof phase transfer catalyzed epoxidation of aliphatic diols usingquaternary ammonium halide catalysts with epichlorohydrin, includingcyclohexanedimethanol.

WO 2009/142901, incorporated herein by reference, describes an epoxyresin composition prepared from a mixture of cis-, trans-1,3- and1,4-cyclohexanedimethanols using several epoxidation processes. WO2009/142901 also discloses examples of preparing various distilledgrades of the monoglycidyl ethers and diglycidyl ethers of cis-,trans-1,3- and 1,4-cyclohexanedimethanols, including a high purity (>99weight percent [wt %]) diglycidyl ether of cis-, trans-1,3- and1,4-cyclohexanedimethanols.

When using the prior art chemistry and processes to manufacturealiphatic and cycloaliphatic epoxy resins via epoxidation of aliphaticand cycloaliphatic hydroxyl-containing materials using an epihalohydrin,it is difficult, if not impossible, to drive to full conversion; and theprocesses produce significant quantities of oligomeric co-products (asmuch as 25 wt %-40 wt % of the epoxy resin composition). The componentsof the epoxy resin may include for example unconverted aliphatic andcycloaliphatic hydroxyl containing material reactant, monoglycidylether, diglycidyl ether, oligomeric co-products, and the like. Whilevarious methods, such as, for example, distillation, are operable forremoving the undesirable oligomeric co-products from the desired highpurity diglycidyl ether of cis-, trans-1,3- and1,4-cyclohexanedimethanols, no satisfactory solution exists for handlingthe resulting separated and isolated oligomeric co-products. Thesolution to date has been to use the as produced mixture of thealiphatic and cycloaliphatic epoxy resins and the oligomeric co-productstogether as a reactive diluent for other epoxy resins where theoligomeric co-products are simply carried into the total diluent andepoxy resin composition. Problems with this approach include preparingan epoxy resin composition having a higher than desirable viscosityinduced by the presence of the oligomeric co-products; and having areduced reactivity with curing agents.

In view of the problems with the prior art processes, it would be highlydesirable to be able to fractionate an aliphatic or cycloaliphatic epoxyresin into monoglycidyl ether, diglycidyl ether, and the like, such thatany residual oligomeric co-products fraction can be advantageouslyutilized in subsequent processes to provide novel thermosettablecompositions and thermosets based on the residual oligomeric co-productsfraction. Such a process and thermosettable compositions and thermosetstherefrom are described in co-pending U.S. Patent Application Ser. No.61/388,059, entitled “THERMOSETTABLE COMPOSITIONS AND THERMOSETSTHEREFROM,” filed of even date herewith by Robert Hefner, Jr. (AttorneyDocket No. 69907), incorporated herein by reference.

While the thermosettable compositions and thermosets based on theresidual oligomeric co-products fraction provide numerous benefits,there is significant room for improvement of the properties provided bysaid compositions. Thus, it would be highly desirable to be able tofractionate an aliphatic or cycloaliphatic epoxy resin into monoglycidylether, diglycidyl ether, and the like, while simultaneously providingnovel epoxy resins, thermosettable compositions and thermosets thereofwith improved properties based on the re-epoxidation of the residualoligomeric fraction.

SUMMARY OF THE INVENTION

A “residual oligomeric product” herein means an oligomeric fractionwhich is co-produced during an epoxidation process for producing analiphatic or cycloaliphatic epoxy resin product; wherein the co-producedoligomeric fraction and the aliphatic or cycloaliphatic epoxy resinproduct resultant mixture after the epoxidation process is subjected toa subsequent separation process such that the co-produced oligomericfraction is separated and isolated from the aliphatic or cycloaliphaticepoxy resin product. The separation process can be carried out by aknown means such as for example a distillation unit operation. Once theco-produced oligomeric fraction is separated from the aliphatic orcycloaliphatic epoxy resin product, for example by distillation, theresulting separated/isolated oligomeric fraction product, typically theresidual bottoms material of a distillation process, comprises theresidual oligomeric product useful in the present invention.

Accordingly, one embodiment of the present invention is directed to anepoxy resin composition including the reaction product of (I) a residualoligomeric product, wherein the residual oligomeric product comprises apolyfunctional aliphatic or cycloaliphatic epoxy (PACE) resin, (II) anepihalohydrin, and (III) a basic-acting substance, in the presence of(IV) a non-Lewis acid catalyst, and (V) optionally, one or moresolvents.

In another embodiment of the present invention, the above epoxy resincomposition is prepared by the process of epoxidizing further (i.e.,“re-epoxidizing”) a PACE resin to produce the novel compositions of thepresent invention. The re-epoxidation process of the present inventionconverts hydroxyl groups present in the PACE resin to glycidyl ethergroups providing increased thermosettable functionality.

Another embodiment of the present invention is directed to athermosettable (curable) epoxy resin composition comprising (a) there-epoxidized epoxy resin composition described above, (b) an epoxyresin curing agent and/or a catalyst, and (c) optionally, an epoxy resincompound other than the epoxy resin composition (a).

Another aspect of the present invention is directed to a process ofpartially thermosetting (B-staging) or completely thermosetting theabove thermosettable epoxy resin compositions.

A further aspect of the present invention is directed to a process ofpreparing the above thermosettable epoxy resin.

Still another embodiment of the present invention is directed to athermoset article prepared by curing the above thermosettable epoxyresin composition.

Upon curing (thermosetting) the epoxy resin composition, a highercrosslink density of the cured thermoset matrix can result. The highercrosslink density can favorably improve the resulting cured productproperties such as its glass transition temperature, resistance tomoisture, resistance to solvents, toughness, and the like. Theconversion of hydroxyl groups to glycidyl ether groups is especiallydesirable to increase resistance to moisture in the cured epoxy resinand increase glass transition temperature as well as reduce viscosity ofthe liquid epoxy resin. Additionally, the process of the presentinvention serves to decrease the amount of undesirable hydrolyzablechloride, if present, via dehydrochlorination of any chlorohydrin groupsin the resultant oligomer fraction.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purpose of illustrating the present invention, the drawings showseveral embodiments of the present invention. However, it should beunderstood that the present invention is not limited to the precisearrangements and instrumentalities shown in the drawings.

FIG. 1 is a schematic flow diagram showing a process of the presentinvention in the production of a re-epoxidized epoxy resin product.

DETAILED DESCRIPTION OF THE INVENTION

Co-pending U.S. Patent Application Ser. No. 61/388,059, (Attorney DocketNo. 69907) discloses a curable polyfunctional aliphatic/cycloaliphaticepoxy resin composition, thermosets thereof, and applications thereforsuch as weatherable coatings. Also, as disclosed in the above patentapplication, because epoxy resins of aliphatic or cycloaliphatic diolscomprise as much as 25 percent (%)-40% oligomer fraction, in order forany project requiring purified diglycidyl ether to be commerciallysuccessful, value must be recovered from this oligomer fraction.

In the present invention, the oligomeric components isolated from a PACEresin are epoxidized further (re-epoxidized) to produce the novelcompositions of the present invention. This re-epoxidation processconverts hydroxyl groups present in the PACE resin to glycidyl ethergroups providing increased thermosettable functionality. Upon curing(thermosetting) this can result in higher crosslink density of the curedthermoset matrix. This can favorably increase glass transitiontemperature, increase resistance to moisture and solvents, increasetoughness, and the like. The conversion of hydroxyl groups to glycidylether groups is especially desirable to increase resistance to moisturein the cured epoxy resin, as well as reduce viscosity of the liquidepoxy resin. Additionally, the re-epoxidation process serves to decreasethe amount of undesirable hydrolyzable chloride, if present, viadehydrochlorination of any chlorohydrin groups in the PACE resin.

The re-epoxidation process of the present invention is expected to bebroadly applicable to upgrade the residual oligomeric product comprisinga polyfunctional aliphatic or cycloaliphatic epoxy resin which may beisolated from the numerous commercially available aliphatic andcycloaliphatic epoxy resins. Of particular interest are the aliphaticand cycloaliphatic epoxy resins produced via non-Lewis acid catalyzedepoxidation of an aliphatic and/or cycloaliphatic hydroxyl-containingcompound or material with an epihalohydrin because of the significantamount of unreacted hydroxyl groups which can be present in the residualoligomeric product fraction isolated from said epoxy resin concomitantwith the minor amount of bound chloromethyl groups present.

The process of the present invention would allow for separation of thevery low viscosity diglycidyl ether useful for advancement reactions ifsufficiently pure as well as a low viscosity reactive diluent for epoxyresins. The remaining oligomer fraction is recovered and re-epoxidizedas per the disclosure of the present invention.

One objective of the present invention is to provide a process includingre-epoxidizing an oligomeric epoxy resin fraction remaining after adistillation unit operation is carried out to substantially recover ahigh purity diglycidyl ether product.

Another objective of the present invention is to use the resultantre-epoxidized epoxy resin composition produced from the re-epoxidationprocess above, to produce thermosettable compositions and thermosetsfrom said thermosettable compositions. This will provide products forfurther use in various applications such as maintenance coatings.

As noted above, the present invention is directed to a novel epoxy resincomposition which is a polyfunctional aliphatic and/or cycloaliphaticepoxy resin composition prepared by re-epoxidizing oligomeric productspresent in an oligomer fraction separated and isolated from an epoxyresin formed by the epoxidation of an aliphatic or cycloaliphatichydroxyl containing material.

One broad embodiment of the present invention comprises a re-epoxidizedepoxy resin composition; wherein the re-epoxidized epoxy resincomposition comprises the reaction product of epoxidizing(re-epoxidizing) a PACE resin which has been separated and isolated froman aliphatic or cycloaliphatic epoxy resin. For example, one embodimentof the present invention comprises a re-epoxidized epoxy resincomposition including the reaction product of (I) a PACE resin, (II) anepihalohydrin, and (III) a basic-acting substance, in the presence of(IV) a non-Lewis acid catalyst, and (V) optionally, one or moresolvents.

As an illustration of a more specific embodiment of the presentinvention, the epoxy resin of an aliphatic or cycloaliphatic diol, suchas, for example, a cis-, trans-1,3- and 1,4-cyclohexanedimethanol (e.g.a commercial cyclohexanedimethanol sold under the trademark of UNOXOL™Diol by The Dow Chemical Company) from a non-Lewis acid catalyzedepoxidation process, typically consists of a minor amount of unreactedaliphatic or cycloaliphatic diol, monoglycidyl ether, diglycidyl ether,and oligomeric products. Distillation methods are typically employed toremove the unreacted aliphatic or cycloaliphatic diol, monoglycidylether, and any other lower boiling materials. [UNOXOL™ cyclic dialcoholis a registered trademark of Union Carbide Corporation.]

The diglycidyl ether is then removed as a product with high enoughpurity, typically 98% or greater, for use in advancement chemistry.After the diglycidyl ether is substantially removed, the polyfunctionaloligomeric product remaining in the distillation pot is recovered. Thus,this specific embodiment of the present invention is based on theproduction of a high purity (≧98%) cycloaliphatic diglycidyl ether,specifically, the diglycidyl ether of UNOXOL™ Diol. For theaforementioned advancement reaction, the oligomeric products must beremoved or else their polyfunctionality induces gelation beforeadvancement can be completed.

While co-pending U.S. Patent Application Ser. No. 61/388,059, (AttorneyDocket No. 69907) provides novel compositions of the PACE resin withcuring agents, thermosets thereof, and applications for the resultantthermosets, the present invention provides novel polyfunctionaloligomeric epoxy resins which are obtained via re-epoxidation. Thepresent invention additionally provides enhanced performance from saidre-epoxidized PACE resins. In one broad embodiment, the presentinvention may be applied to any epoxy resin of an aliphatic orcycloaliphatic hydroxyl-containing material or compound. The process ofthe present invention can benefit and be applied widely to existingnumerous commercial processes that produce aliphatic and cycloaliphaticepoxy resins.

Component (I) is a residual oligomeric product; wherein the residualoligomeric product comprises a PACE resin. For example the PACE resincan be a co-product (or a secondary product) resulting from a firstepoxidation reaction carried out to produce a primary epoxy resinproduct. The PACE resin co-product is separated from and isolated fromthe primary epoxy resin product formed as a result of the epoxidationprocess. The epoxidation process which produces the primary epoxy resinproduct and the PACE resin co-product comprises a reaction employing thefollowing components: (A) an aliphatic or cycloaliphatichydroxyl-containing material, (B) an epihalohydrin, (C) a basic-actingsubstance, (D) a non-Lewis acid catalyst, and (E) optionally, one ormore solvents

The oligomeric product or PACE resin in general is an epoxy resinprecursor as one reactant for the re-epoxidation process of the presentinvention. The PACE resin is obtained via isolation from an aliphatic orcycloaliphatic epoxy resin formed by the epoxidation of (i) an aliphaticor cycloaliphatic hydroxyl containing material using (ii) anepihalohydrin, (iii) a basic-acting substance, (iv) a non-Lewis acidcatalyst, and (v) optionally one or more solvents.

The term “aliphatic or cycloaliphatic polyfunctional epoxy resin”, alsoreferred to herein interchangeably as “oligomeric product or co-product”or simply “oligomer”, as used herein means the product isolated from anepoxy resin formed by the epoxidation of (i) an aliphatic orcycloaliphatic hydroxyl containing material using (ii) an epihalohydrin,(iii) a basic-acting substance, (iv) a non-Lewis acid catalyst, and (v)optionally one or more solvents. Said isolated product comprises theproduct remaining after removal of all (1) “light” components, such as,for example, solvents used in the epoxidation reaction, if any,unreacted epihalohydrin, and co-products such as di(epoxypropyl)ether;(2) unreacted aliphatic or cycloaliphatic hydroxyl containing material,if any; removal of (3) partially epoxidized aliphatic or cycloaliphatichydroxyl containing material, such as, for example, monoglycidyl ether;and substantial removal of (4) fully epoxidized aliphatic orcycloaliphatic hydroxyl containing material, such as, for example,diglycidyl ether, such that the PACE resin product remaining contains nomore than 20 wt % of said fully epoxidized aliphatic or cycloaliphatichydroxyl containing material.

Some representative specific classes of aliphatic or cycloaliphatichydroxyl-containing reactants, component (A) or (i), which may beemployed in the epoxidation to produce the PACE resin precursor to there-epoxidation product of the present invention include for example thefollowing:

The aliphatic or cycloaliphatic hydroxyl-containing reactant useful inthe present invention may include for example cyclohexanedialkanols andcyclohexenedialkanols having the following chemical structures:

(a) Cyclohexanedialkanols and Cyclohexenedialkanols

where each R¹ is independently —H or a C₁ to C₆ alkylene radical(saturated divalent aliphatic hydrocarbon radical), each R² isindependently a C₁ to C₁₂ alkyl or alkoxy radical, a cycloalkyl orcycloalkoxy radical, or an aromatic ring or inertly substituted aromaticring; each q independently has a value of 0 or 1; and v has a value of 0to 2.

Representative examples of the cyclohexanedialkanols andcyclohexenedialkanols include UNOXOL™ Diol (cis-, trans-1,3- and1,4-cyclohexanedimethanol), cis-, trans-1,2-cyclohexanedimethanol; cis-,trans-1,3-cyclohexanedimethanol; cis-, trans-1,4-cyclohexanedimethanol;a methyl substituted cyclohexanedimethanol, such as, for example, a4-methyl-1,2-cyclohexanedimethanol or4-methyl-1,1-cyclohexanedimethanol; 1,1-cyclohexanedimethanol; acyclohexenedimethanol such as, for example,3-cyclohexene-1,1-dimethanol; 3-cyclohexene-1,1-dimethanol, 6-methyl-;4,6-dimethyl-3-cyclohexene-1,1-dimethanol;cyclohex-2-ene-1,1-dimethanol; 1,1-cyclohexanediethanol;1,4-bis(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexanediethanol; mixturesthereof and the like. Included within this class of epoxy resins are thecyclohexanedioxyalkanols and cyclohexenedioxyalkanols, where at leastone q has a value of 1. Specific examples include1,4-(2-hydroxyethyloxy)cyclohexane and1,4-(2-hydroxyethyloxy)cyclohex-2-ene. All possible geometric isomersare intended by the formulas and in the aforementioned list, even if theisomers are not explicitly shown or given.

A representative synthesis of 1,1-cyclohexanedimethanol is given byManea, et al, Paint and Coatings Industry, Aug. 1, 2006, incorporatedherein by reference in its entirety. A representative synthesis of3-cyclohexene-1,1-dimethanol is described in U.S. Pat. No. 6,410,807,incorporated herein by reference.

UNOXOL™ Diol (cis-, trans-1,3- and 1,4-cyclohexanedimethanol) is apreferred cyclohexanedialkanol. As used herein, the term “cis-,trans-1,3- and -1,4-cyclohexanedimethylether moiety” means a structureor a blend of chemical structures comprising four geometric isomers, acis-1,3-cyclohexanedimethylether, a trans-1,3-cyclohexanedimethyletherstructure, a cis-1,4-cyclohexanedimethylether, and atrans-1,4-cyclohexanedimethylether, within an epoxy resin. The fourgeometric isomers are shown in the following structures:

A detailed description of the epoxy resins comprising the cis-,trans-1,3- and 1,4-cyclohexanedimethylether moiety and the processes forpreparing the same is provided in the aforementioned WO2009/142901.Phase transfer catalyzed epoxidation of aliphatic diols using quaternaryammonium halide catalysts with epichlorohydrin to produce aliphaticepoxy resins with properties that are superior to the correspondingaliphatic epoxy resins produced via Lewis acid catalyzed coupling withepichlorohydrin is described in aforementioned EP Patent No. 0 121 260.Included are epoxy resins prepared from cyclohexanedimethanol anddicyclopentadienedimethanol (isomers unspecified).

The aliphatic or cycloaliphatic hydroxyl-containing reactant useful inthe present invention may include for example one or morecyclohexanolmonoalkanols and cyclohexenolmonoalkanols having thefollowing chemical structures:

(b) Cyclohexanolmonoalkanols and Cyclohexenolmonoalkanols

where each R¹, R², q and v are as hereinbefore defined.

Representative examples of the cyclohexanolmonoalkanols andcyclohexenolmonoalkanols which are aliphatic/cycloaliphatic hybrid diolstructures containing one cyclohexanol or cyclohexenol moiety and onemonoalkanol moiety, such as, for example, a monomethanol moiety,include, for example, 1-(hydroxymethyl)-cyclohexanol,1-(hydroxymethyl)cyclohex-3-enol, 3-hydroxymethylcyclohexanol,4-hydroxymethylcyclohexanol,rac-1-isopropyl-4-methyl-2-cyclohexene-1alpha,2alpha-diol;5beta-isopropyl-2-methyl-3-cyclohexene-1alpha,2alpha-diol;2-hydroxymethyl-1,3,3-trimethyl-cyclohexanol; cyclohexanol,1-(2-hydroxyethoxy); mixtures thereof and the like. All possiblegeometric isomers are intended by the formulas and in the aforementionedlist, even if the isomers are not explicitly shown or given.

Another example of such compounds is trans-2-(hydroxymethyl)cyclohexanolprepared by Prins reaction on cyclohexane by Kazunari Taira et al,Journal of the American Chemical Society, 106, 7831-7835 (1984),incorporated herein by reference. A second example is1-phenyl-cis-2-hydroxymethyl-r-1-cyclohexanol disclosed in U.S. Pat. No.4,125,558, incorporated herein by reference. A third example istrans-4-(hydroxymethyl)cyclohexanol reported by Tamao et al., OrganicSyntheses, Collective Volume 8, p. 315, Annual Volume 69, p. 96,incorporated herein by reference.

The aliphatic or cycloaliphatic hydroxyl-containing reactant useful inthe present invention may include for example one or moredecahydronaphthalenedialkanols, octahydronaphthalenedialkanols and1,2,3,4-tetrahydronaphthalenedialkanols having the following chemicalstructures:

(c) Decahydronaphthalenedialkanols, Octahydronaphthalenedialkanols and1,2,3,4-Tetrahydronaphthalenedialkanols

where each R¹, R², q and v are as hereinbefore defined.

Representative examples of the decahydronaphthalenedialkanols,octahydronaphthalenedialkanols and1,2,3,4-tetrahydronaphthalenedialkanols containing onedecahydronaphthalenedialkanol, octahydronaphthalenedialkanol or1,2,3,4-tetrahydronaphthalenedialkanol moiety, include1,2-decahydronaphthalenedimethanol; 1,3-decahydronaphthalenedimethanol;1,4-decahydronaphthalenedimethanol; 1,5-decahydronaphthalenedimethanol;1,6-decahydronaphthalenedimethanol; 2,7-decahydronaphthalenedimethanol;1,2,3,4-tetrahydronaphthalenedimethanol (tetralin dimethanol);1,2-octahydronaphthalenedimethanol; 2,7-octahydronaphthalenedimethanol;4-methyl-1,2-decahydronaphthalenedimethanol;4,5-dimethyl-2,7-decahydronaphthalenedimethanol;1,2-decahydronaphthalenediethanol; 2,7-decahydro-naphthalenediethanol;mixtures thereof and the like. All possible geometric isomers areintended by the formulas and in the aforementioned list, even if theisomers are not explicitly shown or given.

While not shown by the structures given above, it is intended that thehybrid diol structures also be included where one monoalkanol moiety isattached to a cycloaliphatic ring and one hydroxyl moiety is directlyattached to a cycloaliphatic ring.

One example of said hybrid structures would be1-hydroxy-2-hydroxymethyldecahydronaphthalene.

The aliphatic or cycloaliphatic hydroxyl-containing reactant useful inthe present invention may include for example one or morebicyclohexanedialkanols or bicyclohexanolmonoalkanols having thefollowing chemical structures:

(d) Bicyclohexanedialkanols or Bicyclohexanolmonoalkanols

where each R¹, R², q and v are as hereinbefore defined.

Representative examples of the bicyclohexanedialkanols orbicyclohexanolmonoalkanols include bicyclohexane-4,4′-dimethanol;bicyclohexane-1,1′-dimethanol; bicyclohexane-1,2-dimethanol,bicyclohexane-4,4′-diethanol; bicyclohexane-1-hydroxy-1′-hydroxymethyl;bicyclohexane-4-hydroxy-4′-hydroxymethyl; mixtures thereof and the like.All possible geometric isomers are intended by the formulas and in theaforementioned list, even if the isomers are not explicitly shown orgiven.

While not shown by the structures given above, it is intended that epoxyresins of bicyclohexenedialkanols or bicyclohexenolmonoalkanols beincluded where either one or both rings may contain a singleunsaturation. One example of said bicyclohexene structures would be theepoxy resin of bicyclohexene-1,1′-dimethanol.

The aliphatic or cycloaliphatic hydroxyl-containing reactant useful inthe present invention may include for example one or more bridgedcyclohexanols having the following chemical structures:

(e) Bridged Cyclohexanols

where each Q is a C₁ to C₁₂ alkylene radical (saturated divalentaliphatic hydrocarbon radical), O, S, O═S═O, S═O, C═O, R³NC═O; R³ is —Hor a C₁ to C₆ alkyl radical (saturated monovalent aliphatic hydrocarbonradical); R² and v are as hereinbefore defined.

Representative examples of the bridged cyclohexanols include thefollowing compounds where the aromatic rings have been hydrogenated tocyclohexane rings: bisphenol A (4,4′-isopropylidenediphenol), bisphenolF (4,4′-dihydroxydiphenylmethane), 4,4′-dihydroxydiphenylsulfone;4,4′-dihydroxybenzanilide; 1,1′-bis(4-hydroxyphenyl)cyclohexane;4,4′-dihydroxydiphenyl oxide; 4,4′-dihydroxybenzophenone;1,1-bis(4-hydroxyphenyl)-1-phenylethane;4,4′-bis(4(4-hydroxyphenoxy)-phenylsulfone)diphenyl ether;2,2′-sulfonyldiphenol; 4,4′-thiodiphenol; dicyclopentadiene diphenol.

(f) Other Cycloaliphatic and Polycycloaliphatic Diols, MonolMonoalkanols, or Dialkanols

Most any cycloaliphatic or polycycloaliphatic diol, monol monoalkanol ordialkanol may be employed in the epoxidation process. Representativeexamples include the dicyclopentadienedimethanols, thenorbornenedimethanols, the norbornanedimethanols, thecyclooctanedimethanols, the cyclooctenedimethanols, thecyclooctadienedimethanols, the pentacyclodecanedimethanols, thebicyclooctanedimethanols, the tricycledecanedimethanols, thebicycloheptenedimethanols, the dicyclopentadienediols, thenorbornenediols, the norbornanediols, the cyclooctanediols, thecyclooctenediols, the cyclooctadienediols, the cyclohexanediols, thecyclohexenediols, cyclopentane-1,3-diol; bicyclopentane-1,1′-diol;decahydronaphthalene-1,5-diol;trans,trans-2,6-dimethyl-2,6-octadiene-1,8-diol;5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane;3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane;3-methyl-2,2-norbornanedimethanol; 5-norbornene-2,3-dimethanol;norbornane-2,3-trans-dimethanol; perhydro-1,4:5,8-dimethanonaphthalene-2,3-trans-dimethanol; perhydro-1,4:5,8:9,10-trimethanoanthracene-2,3-trans-dimethanol; and 5-norbornene-2,3-dimethanol;norbornanolmonomethanols; and norbornenols.

Preparation of norbornane-2,3-trans-dimethanol;perhydro-1,4:5,8-dimethanonaphthalene-2,3-trans-dimethanol; andperhydro-1,4:5,8:9,10-trimethanoanthracene-2,3-trans-dimethanol arereported by Wilson et al., Journal of Polymer Science Polymer ChemistryEdition, volume 10, 3191-3204 (1972), incorporated herein by reference.Preparation of 5-norbornene-2,3-dimethanol is reported by HitoshiNakamura et al, Macromolecules, 23, 3032-3035 (1990), incorporatedherein by reference.

(g) Aliphatic Hydroxyl-Containing Materials

Most any aliphatic hydroxyl containing reactant may be employed in theepoxidation process. Representative of the aliphatic hydroxyl containingreactants include alkoxylated phenolic reactants, such as, for example,ethoxylated catechol, ethoxylated resorcinol, ethoxylated hydroquinone,and ethoxylated bisphenol A. Alkoxylation products of the hydrogenatedaromatic phenolic reactants include ethoxylated hydrogenated bisphenolA. Other aliphatic hydroxyl containing reactants include neopentylglycol, trimethylol propane, ethylene glycol, propylene glycol,triethylene glycol, higher alkoxylated ethylene glycols,pentaerythritol, 1,4-butanediol; 1,6-hexanediol; and 1,12-dodecandiol.

Epihalohydrins which may be employed in the epoxidation to produce thePACE resin precursor to the re-epoxidation product of the presentinvention and also in the re-epoxidation process, include, for example,epichlorohydrin, epibromohydrin, epiiodohydrin, methylepichlorohydrin,methylepibromohydrin, methylepiiodohydrin, and any combination thereof.Epichlorohydrin is the preferred epihalohydrin.

The ratio of the epihalohydrin to the aliphatic or cycloaliphatichydroxyl containing material for the epoxidation process to produce thePACE resin precursor is generally from about 1:1 to about 25:1,preferably from about 1.8:1 to about 10:1, and more preferably fromabout 2:1 to about 5:1 equivalents of epihalohydrin per hydroxyl groupin the aliphatic or cycloaliphatic hydroxyl containing material. Theterm “hydroxyl group” used herein refers to the hydroxyl groups derivedfrom the aliphatic or cycloaliphatic hydroxyl containing material. Thusthe hydroxyl group differs from a secondary hydroxyl group formed duringthe process of the forming the halohydrin intermediate to the aliphaticor cycloaliphatic hydroxyl containing material.

For the re-epoxidation of the PACE resin precursor, the ratio of theepihalohydrin per hydroxyl group is generally from about 1:1 to about100:1, preferably from about 1.8:1 to about 20:1, and more preferablyfrom about 2:1 to about 10:1 equivalents of epihalohydrin per hydroxylgroup be employed, where the term “hydroxyl group” includes any hydroxylgroups derived from the aliphatic or cycloaliphatic hydroxyl containingmaterial which have not been epoxidized, as well as the secondaryhydroxyl groups formed during the process of the forming the halohydrinintermediate to the aliphatic or cycloaliphatic hydroxyl containingmaterial which have not been epoxidized.

Basic acting substances which may be employed in the epoxidation toproduce the PACE resin precursor to the re-epoxidation product of thepresent invention and also in the re-epoxidation process include alkalimetal hydroxides, alkaline earth metal hydroxides, carbonates,bicarbonates, and any mixture thereof, and the like. More specificexamples of the basic acting substance include sodium hydroxide,potassium hydroxide, lithium hydroxide, calcium hydroxide, bariumhydroxide, magnesium hydroxide, manganese hydroxide, sodium carbonate,potassium carbonate, lithium carbonate, calcium carbonate, bariumcarbonate, magnesium carbonate, manganese carbonate, sodium bicarbonate,potassium bicarbonate, magnesium bicarbonate, lithium bicarbonate,calcium bicarbonate, barium bicarbonate, manganese bicarbonate, and anycombination thereof. Sodium hydroxide and/or potassium hydroxide are thepreferred basic acting substance.

Non-Lewis acid catalysts which may be employed in the epoxidation toproduce the PACE resin precursor to the re-epoxidation product of thepresent invention and also in the re-epoxidation process include, forexample, ammonium, phosphonium, or sulfonium salts. More specificexamples of the catalyst include salts of the following ammonium,phosphonium and sulfonium cations: benzyltributylammonium,benzyltriethylammonium, benzyltrimethylammonium, tetrabutylammonium,tetraoctylammonium, tetramethylammonium, tetrabutylphosphonium,ethyltriphenylphosphonium, triphenylsulfonium,4-tert-butoxyphenyldiphenylsulfonium,bis(4-tert-butoxyphenyl)phenylsulfonium,tris(4-tert-butoxyphenyl)sulfonium,3-tert-butoxyphenyldiphenylsulfonium,bis(3-tert-butoxyphenyl)phenylsulfonium,tris(3-tert-butoxyphenyl)sulfonium,3,4-di-tert-butoxyphenyldiphenylsulfonium,bis(3,4-di-tert-butoxyphenyl)phenylsulfonium,tris(3,4-di-tert-butoxyphenyl)sulfonium,diphenyl(4-thiophenoxyphenyl)sulfonium,4-tert-butoxycarbonylmethyloxy-phenyldiphenylsulfonium,tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium,(4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium,tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium,(4-n-hexyloxy-3,5-dimethylphenyl)diphenylsulfonium,dimethyl(2-naphthyl)sulfonium, 4-methoxyphenyldimethylsulfonium,trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium,trinaphthylsulfonium, tribenzylsulfonium, diphenylmethylsulfonium,dimethylphenylsulfonium, 2-oxo-2-phenylethylthiacyclopentanium,diphenyl-2-thienylsulfonium, 4-n-butoxynaphthyl-1-thiacyclopentanium,2-n-butoxynaphthyl-1-thiacyclopentanium,4-methoxynaphthyl-1-thiacyclopentanium, and2-methoxynaphthyl-1-thiacyclopentanium. Preferred cations aretriphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium,4-tert-butoxyphenyldiphenylsulfonium, tris(4-tert-butylphenyl)sulfonium,tris(4-tert-butoxyphenyl)sulfonium, dimethylphenylsulfonium, and anycombination thereof. Suitable quaternary phosphonium catalysts alsoinclude, for example, the quaternary phosphonium compounds disclosed inU.S. Pat. Nos. 3,948,855; 3,477,990 and 3,341,580; and Canadian PatentNo. 858,648, all of which are incorporated herein by reference.Benzyltriethylammonium halides are the preferred catalyst, withbenzyltriethylammonium chloride being most preferred.

While the amount of catalyst may vary due to factors such as reactiontime and reaction temperature, the lowest amount of catalyst required toproduce the desired effect is preferred. In general, the catalyst may beused in an amount of from about 0.5 wt % to about 25 wt %, preferably,from about 1 wt % to about 18 wt %, and more preferably, from about 2 wt% to about 12 wt %, based on the total weight of the aliphatic orcycloaliphatic hydroxyl containing material epoxidized to produce thePACE resin precursor to the re-epoxidation product of the presentinvention and also in the re-epoxidation process.

The epihalohydrin may function as both a solvent and a reactant in theepoxidation. Alternatively, a solvent other than the epihalohydrin mayalso be used in the process for preparing the PACE resin (A). Thesolvent other than the epihalohydrin should be inert to any materialsused in the process of preparing the PACE resin (A), including forexample, reactants, catalysts, intermediate products formed during theprocess, and final products. Solvents which may optionally be employedin the epoxidation process include, for example, aliphatic and aromatichydrocarbons, halogenated aliphatic hydrocarbons, aliphatic ethers,aliphatic nitriles, cyclic ethers, ketones, amides, sulfoxides, tertiaryaliphatic alcohols, and any combination thereof.

Particularly preferred solvents include pentane, hexane, octane,toluene, xylene, methylethylketone, methylisobutylketone,dimethylsulfoxide, diethyl ether, tetrahydrofuran, 1,4-dioxane,dichloromethane, chloroform, ethylene dichloride, methyl chloroform,ethylene glycol dimethyl ether, acetonitrile, tertiary-butanol,N,N-dimethylformamide; N,N-dimethylacetamide; and any combinationthereof.

If the solvent other than the epihalohydrin is employed in theepoxidation process, the minimum amount of solvent needed to achieve thedesired result is preferred. In general, the solvent may be present inthe process from about 5 wt % to about 250 wt %, preferably, about 20 wt% to about 180 wt %, and more preferably, about 40 wt % to about 120 wt%, based on the total weight of the aliphatic or cycloaliphatic hydroxylcontaining material. The solvent may be removed from the final productat the completion of the reaction of forming the epoxy resin usingconventional methods, such as vacuum distillation.

A specific example of the PACE resin is the aliphatic/cycloaliphaticpolyfunctional epoxy resin isolated from the epoxy resin of cis-,trans-1,3- and 1,4-cyclohexanedimethanol. It is to be understood thatthe PACE resin comprises multiple components. For the PACE resinisolated from the epoxy resin of cis-, trans-1,3- and1,4-cyclohexanedimethanol, the following components have been identifiedand may or may not be present in the individual products depending onthe chemistry and processing employed to produce said epoxy resin(geometrical isomers and substitution are not shown in the chemicalstructures, the multiple geometrical isomers that are present are notgiven by the chemical names, other unidentified components may bepresent):

-   2-propanol, 1-(oxiranylmethoxy)-3-[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-

-   oxirane, 2-[[[3(or    4)-[[2,3-bis(oxiranylmethoxy)propoxy]methyl]cyclohexyl]methoxy]methyl]-

-   oxirane, 2-[[2-chloro-1-[[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]-

-   cyclohexanemethanol, 3(or 4)-[[2-hydroxy-3-[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]propoxy]methyl]-

-   2-propanol, 1,3-bis[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-

-   oxirane, 2-[[2-[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-1-[[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]-    A minor amount of 3 isomeric monochloro compounds co-elute with this    latter triglycidyl ether.

Re-epoxidation of the PACE resin is used to beneficially modify thedistribution of the components comprising said epoxy resin. Thus in thepresent specific example of the new compositions from the re-epoxidationof the PACE resin, the re-epoxidation process converts the diglycidylethers with a secondary hydroxyl group in their backbone to thecorresponding triglycidyl ethers:

While the goal of the re-epoxidation process for most intendedapplications would be to fully convert the monohydroxy functionaldiglycidyl ethers to the corresponding triglycidyl ethers, respectively,via selective epoxidation of the secondary hydroxyl groups in therespective backbones, it is also operable to only partially convertthese monohydroxy functional diglycidyl ethers to the correspondingtriglycidyl ethers.

Thus, in the re-epoxidation process of the present invention, theisolated oligomer fraction is subjected to further epoxidation toproduce the epoxy resin of the present invention. In this re-epoxidationprocess, oligomeric components of the PACE resin which are partiallyepoxidized, that is, they possess free hydroxyl functionality, arefurther epoxidized. Minor amounts of chlorohydrin intermediates, if any,may also be converted to epoxide functionality.

The epoxy resin composition of the present invention is prepared by are-epoxidation process comprising reacting Component (I), the PACE resindescribed above, with (II) an epihalohydrin, and (III) a basic-actingsubstance, in the presence of (IV) a non-Lewis acid catalyst and,optionally (V) one or more solvents. Component (II) can include any ofthe epihalohydrins described above with reference to epihalohydrinscomponent (B); Component (III) can include any of the basic-actingsubstances described above with reference to basic-acting substancescomponent (C); and Component (IV) can include any of the non-Lewis acidcatalysts described above, with reference to non-Lewis acid catalystscomponents (D). Any of the solvents described above with reference tocomponent (E) may also be added to the reaction mixture containingcomponents (I)-(IV).

In the carrying out the process of the present invention, the PACE resincomposition useful in the present invention is first produced as asecond product stream during the production of a first epoxy resinproduct stream by epoxidizing an aliphatic or cycloaliphatic hydroxylcontaining material, particularly an aliphatic or cycloaliphatic diolsuch as described herein or in WO2009/142901. After the epoxidationreaction, the PACE resin composition (second epoxy resin product stream)is separated and isolated from the first epoxy resin product stream.

The first and second epoxy products are formed by epoxidizing (i) analiphatic or cycloaliphatic hydroxyl containing material with (ii) anepihalohydrin, (iii) a basic-acting substance, (iv) a non-Lewis acidcatalyst, and optionally, (v) one or more solvents.

With reference to FIG. 1, there is shown a general process formanufacturing an epoxy resin composition of the present invention, theprocess generally indicated by reference numeral 100. FIG. 1 shows afirst series of epoxidation stages, 110, 130, and 150 followed by awashing step after each epoxidation stage including washing stages 120,140 and 160, respectively. FIG. 1 also shows a second series ofepoxidation stages, 180 and, 210 followed by a washing step after eachstage including 190 and 220, respectively. It should be understood thatthe number of epoxidation stages and washing steps used in presentinvention process may comprise one, two or more stages and the presentinvention is not limited to the embodiment shown in FIG. 1 which showsthree epoxidation stages and three wash steps as a first series and twosubsequent epoxidation stages and two wash steps as a second series. Inother embodiments, two or more stages or steps of the present inventionmay be combined and carried out by one apparatus or by two or moreseparate apparatuses.

With reference to FIG. 1 again, the process 100 includes an aliphatic orcycloaliphatic hydroxyl containing material feed stream 111, anepihalohydrin feed stream 112, a non-Lewis acid catalyst feed stream113, and a solvent stream 114 along with a basic-acting substance feedstream 115 and an inert gas such as a nitrogen stream 116 are fed intothe first epoxidation reaction stage 110 to carry out a firstepoxidation reaction. After the first epoxidation reaction, a resultantfirst epoxidation product, stream 117 from first stage 110, is washedwith a water stream 121 at the first washing stage 120 as an aqueouswaste stream 122 is directed to a waste recovery operation (not shown)or to another operation for further processing. A washed epoxidationproduct stream 123 exits from the first washing stage 120.

The washed epoxidation product stream 123 from the first washing stage120 is forwarded to a second epoxidation stage 130 wherein a secondnon-Lewis acid catalyst feed stream 131, a second basic-acting substancefeed stream 132 and a second inert gas such as a nitrogen stream 133 arefed into the second epoxidation reaction stage 130 to carry out furtherepoxidation of the washed epoxidation product stream 123 from the firstwashing stage 120 to form a second epoxidation product stream 134. In anoptional embodiment, a second epihalohydrin stream (not shown) and asecond solvent stream (not shown) made be fed into the secondepoxidation stage 130 if desired. After the second epoxidation reaction,the resultant second epoxidation product, stream 134 from second stage130, is washed with a water stream 141 at the second washing stage 140as an aqueous waste stream 142 is directed to a waste recovery operation(not shown) or to another operation for further processing. A washedepoxidation product stream 143 exits from the second washing stage 140.

The washed epoxidation product stream 143 from the second washing stage140 is forwarded to a third epoxidation stage 150 wherein a thirdnon-Lewis acid catalyst feed stream 151, a third basic-acting substancefeed stream 152 and a third inert gas such as a nitrogen stream 153 arefed into the third epoxidation reaction stage 150 to carry out furtherepoxidation of washed epoxidation product stream 143 from the secondwashing stage 140 to form a third epoxidation product stream 154. In anoptional embodiment, a third epihalohydrin stream (not shown) and athird solvent stream (not shown) made be fed into the second epoxidationstage 150 if desired. After the third epoxidation reaction, theresultant epoxidation product, stream 154 from the third stage 150, iswashed with a water stream 161 at the third washing stage 160 as anaqueous waste stream 162 is directed to a waste recovery operation (notshown) or to another operation for further processing. A washedepoxidation product stream 163 exits from the third washing stage 160.

Optionally, in one embodiment, the washed epoxidation product stream 163from the third washing stage 160 may be forwarded to a devolatilizationoperation (not shown) to remove any lights (not shown) from the washedepoxidation product 163 to form a crude epoxidation product stream (notshown). In the embodiment shown in FIG. 1, the washed epoxidationproduct stream 163 is forwarded to a fractionation operation 170 whereina top lights stream 171, a bottoms stream 172, a partially orpartially/fully epoxidized aliphatic or cycloaliphatic hydroxylcontaining material stream 173, and a fully epoxidized aliphatic orcycloaliphatic hydroxyl containing material stream 174 are produced. Thefully epoxidized aliphatic or cycloaliphatic hydroxyl containingmaterial stream 174 is a purified epoxy resin product which can be usedin subsequent processes. The bottoms stream 172 in this embodiment is anexample of a polyfunctional aliphatic or cycloaliphatic epoxy (PACE)resin useful in the present invention.

In the present invention, the bottoms stream 172 is forwarded to asecond series of epoxidation stages including a fourth epoxidation stage180 and a fifth epoxidation stage 210. The bottoms stream 172, anepihalohydrin feed stream 181, a fourth non-Lewis acid catalyst feedstream 182, a solvent stream 183, a fourth basic-acting substance feedstream 184, and a fourth inert gas such as a nitrogen stream 185 are fedinto the fourth epoxidation reaction stage 180 to carry out furtherepoxidation of the bottoms stream 172 exiting from the fractionationoperation 170 to form a fourth epoxidation product stream 186. After thefourth epoxidation reaction, the resultant epoxidation product, stream186 from fourth stage 180, is washed with a water stream 191 at thefourth washing stage 190 as an aqueous waste stream 192 is directed to awaste recovery operation (not shown) or to another operation for furtherprocessing. A washed epoxidation product stream 193 exits from thefourth washing stage 190.

The washed epoxidation product stream 193 from the fourth washing stage190 is forwarded to a fifth epoxidation stage 210 wherein a fifthnon-Lewis acid catalyst feed stream 211, a fifth basic-acting substancefeed stream 212 and a fifth inert gas such as a nitrogen stream 213 arefed into the fifth epoxidation reaction stage 210 to carry out furtherepoxidation of the washed epoxidation product stream 193 from the fourthwashing stage 190 to form a fifth epoxidation product stream 214. In anoptional embodiment, an epihalohydrin stream (not shown) and a solventstream (not shown) made be fed into the fifth epoxidation stage 210 ifdesired. After the fifth epoxidation reaction, the resultant epoxidationproduct, stream 214 from the fifth stage 210, is washed with a waterstream 221 at a fifth washing stage 220 as an aqueous waste stream 222is directed to a waste recovery operation (not shown) or to anotheroperation for further processing. A washed epoxidation product stream223 exits from the fifth washing stage 210.

The washed epoxidation product stream 223 from the fifth washing stage220 is forwarded to a devolatilization operation 230 to remove anylights 231 from the washed epoxidation product and to form are-epoxidized product stream 232. Although not shown, in one embodiment,the re-epoxidation product stream 232 may be forwarded to a blendingoperation to be blended with a curing agent stream to form a curablecomposition. The resultant curable composition may subsequently be curedto form a thermoset. Optionally, any other additive stream, for examplean epoxy resin other than the re-epoxidized PACE resin, may be blendedwith the epoxidation product stream 232 and curing agent stream to formthe curable composition.

It should be understood that any conventional equipment known to thoseskilled artisans can be used to carry out the manufacturing process ofthe present invention. For example, the equipment can includeepoxidation reactor vessels; evaporation vessels such as rotaryevaporators; and separation vessels such as distillation apparatus;which are known in the art. For example, generally, a separation vessel,such as a fractional vacuum distillation apparatus 170 may be used toproduce several fractionation cuts including a “lights” stream 171, a“bottoms” stream 172 comprising unrecovered fully epoxidized aliphaticor cycloaliphatic hydroxyl containing material and oligomers, a streamof partially or partially/fully epoxidized aliphatic or cycloaliphatichydroxyl containing mixtures 173, and a stream of high purity fullyepoxidized aliphatic or cycloaliphatic hydroxyl containing materialproduct 174. The bottoms stream 172 is separated and isolated from theother streams leaving the distillation apparatus. The high purity fullyepoxidized aliphatic or cycloaliphatic hydroxyl containing materialproduct stream shown in FIG. 1 as stream 174 may be forwarded to asubsequent process to form curable compositions and thermosetstherefrom. In one embodiment, the bottoms stream 172 may also beforwarded to a subsequent process to form curable compositions andthermosets therefrom. In the embodiment shown in FIG. 1, the bottomsstream 172 is re-epoxidized by the process and equipment described aboveto form the re-epoxidized product stream 232 of the present invention.

Another embodiment of the present invention concerns a thermosettable(curable) epoxy resin composition comprising (A) a polyfunctionalaliphatic and/or cycloaliphatic epoxy resin composition prepared byre-epoxidizing oligomeric products present in an oligomer fractionseparated and isolated from an epoxy resin formed by the epoxidation ofan aliphatic or cycloaliphatic hydroxyl containing material using (1) abasic-acting substance, (2) non-Lewis acid catalyst, and (3) anepihalohydrin, and optionally, (4) one or more solvents; (B) an epoxyresin curing agent and/or an epoxy resin curing catalyst; and (C)optionally, an epoxy resin compound other than the re-epoxidized PACEresin (A).

The term “curable” (also referred to as “thermosettable”) means that thecomposition is capable of being subjected to conditions which willrender the composition to a cured or thermoset state or condition. Theterm “cured” or “thermoset” is defined by L. R. Whittington inWhittington's Dictionary of Plastics (1968) on page 239 as follows:“Resin or plastics compounds which in their final state as finishedarticles are substantially infusible and insoluble. Thermosetting resinsare often liquid at some stage in their manufacture or processing, whichare cured by heat, catalysis, or some other chemical means. After beingfully cured, thermosets cannot be resoftened by heat. Some plasticswhich are normally thermoplastic can be made thermosetting by means ofcrosslinking with other materials.”

The thermosettable epoxy resin composition of the present invention isprepared by admixing (a) the re-epoxidized PACE resin composition of thepresent invention, with (b) an epoxy resin curing agent and/or a curingcatalyst; and (c) optionally, an epoxy resin other than there-epoxidized PACE resin composition (a) of the present invention. Thecuring agent and/or curing catalyst are used in amounts which willeffectively thermoset the curable epoxy resin composition, with theunderstanding that the amounts will depend upon the specificre-epoxidized PACE resin, any optionally used epoxy resin, and thecuring agent and/or catalyst employed.

Generally, the ratio of the curing agent and the re-epoxidized PACEresin and epoxy resin other than the re-epoxidized PACE resin if used isfrom about 0.60:1 to about 1.50:1, and preferably from about 0.95:1 toabout 1.05:1 equivalents of reactive hydrogen atom present in the curingagent per equivalent of epoxide group in the epoxy resin(s) at theconditions employed for curing.

A preferred curable epoxy resin composition of the present inventioncomprises an aliphatic and/or cycloaliphatic curing agent and there-epoxidized PACE resin. The curable epoxy resin composition, whencured, provides a cured epoxy resin free of any aromatic group.

A more specific preferred curable epoxy resin composition of the presentinvention comprises an alkyleneamine (polyalkylenepolyamine) curingagent, such as, for example, ethylenediamine, diethylenetriamine ortriethylenetetramine and the re-epoxidized PACE resin. The curable epoxyresin composition, when cured, provides a cured epoxy resin free of anyaromatic group.

Another preferred curable epoxy resin composition of the presentinvention comprises the (1) aliphatic and/or cycloaliphatic curingagent, (2) the re-epoxidized PACE resin and (3) an epoxy resin otherthan the PACE resin wherein the epoxy resin (3) comprises one or more ofaliphatic and/or cycloaliphatic epoxy resins. The curable epoxy resincomposition, when cured, provides a cured epoxy resin free of anyaromatic group.

A more specific preferred curable epoxy resin composition of the presentinvention comprises (1) an alkyleneamine (polyalkylenepolyamine) curingagent, (2) the re-epoxidized PACE resin and (3) an epoxy resin otherthan the re-epoxidized PACE resin wherein the epoxy resin (3) comprisesone or more of aliphatic and/or cycloaliphatic epoxy resins. The curableepoxy resin composition, when cured, provides a cured epoxy resin freeof any aromatic group.

The epoxy resin curing agent and/or curing catalyst used in the presentinvention to form the thermosettable mixture with the re-epoxidized PACEresin comprises at least one material having two or more reactivehydrogen atoms per molecule. The reactive hydrogen atoms are reactivewith epoxide groups, such as those epoxide groups contained in there-epoxidized PACE resin.

Certain of the hydrogen atoms can be non-reactive with the epoxidegroups in the initial process of forming the cured product but reactivein a later process of curing the epoxy resin, when there are otherfunctional groups, which are much more reactive with the epoxide groupsunder reaction conditions used, present in the B-staging orthermosetting reaction of forming the thermoset product. For example, areactive compound may have two different functional groups each bearingat least one reactive hydrogen atom, with one functional group beinginherently more reactive with an epoxide group than the other under thereaction conditions used. These reaction conditions may include the useof a catalyst which favors a reaction of the reactive hydrogen atom(s)of one functional group with an epoxide group over a reaction of thereactive hydrogen atom(s) of the other functional group with an epoxidegroup. The catalyst may also be latent, for example under conditions ofmixing the thermosettable mixture, then activated at a later time, forexample by heating of the latently catalyzed thermosettable mixture.

Other non-reactive hydrogen atoms may also include hydrogen atoms in thesecondary hydroxyl groups which form during an epoxide ring openingreaction in the process of producing the partially cured or fully curedproduct.

The curing agent may further comprise aliphatic, cycloaliphatic and/oraromatic groups within the curing agent structure. The aliphatic groupsmay be branched or unbranched. The aliphatic or cycloaliphatic groupsmay also be saturated or unsaturated and may comprise one or moresubstituents which are inert (not reactive) to the process of preparingthe thermosettable compositions and thermosets of the present invention.The substituents may be attached to a terminal carbon atom or may bebetween two carbon atoms, depending on the chemical structures of thesubstituents. Examples of such inert substituents include halogen atoms,preferably chlorine or bromine, nitrile, nitro, alkyloxy, keto, ether(—O—), thioether (—S—), or tertiary amine. The aromatic ring, if presentwithin the curing agent structure, may comprise one or more heteroatomssuch as N, O, S and the like.

Examples of the curing agent may include compounds such as (a) di- andpolyphenols, (b) di- and polycarboxylic acids, (c) di- andpolymercaptans, (d) di- and polyamines, (e) primary monoamines, (f)sulfonamides, (g) aminophenols, (h) aminocarboxylic acids, (i) phenolichydroxyl containing carboxylic acids, (j) sulfanilamides, and (k) anycombination of any two or more of such compounds or the like.

Examples of the di- and polyphenols (a) include 1,2-dihydroxybenzene(catechol); 1,3-dihydroxybenzene (resorcinol); 1,4-dihydroxybenzene(hydroquinone); 4,4′-isopropylidenediphenol (bisphenol A);4,4′-dihydroxydiphenylmethane; 3,3′,5,5′-tetrabromobisphenol A;4,4′-thiodiphenol; 4,4′-sulfonyldiphenol; 2,2′-sulfonyldiphenol;4,4′-dihydroxydiphenyl oxide; 4,4′-dihydroxybenzophenone;1,1′-bis(4-hydroxyphenyl)-1-phenylethane; 3,3′,5,5′-tetrachlorobisphenolA; 3,3′-dimethoxybisphenol A;3,3′,5,5′-tetramethyl-4,4′-dihydroxydiphenyl; 4,4′-dihydroxybiphenyl;4,4′-dihydroxy-alpha-methylstilbene; 4,4′-dihydroxybenzanilide;4,4′-dihydroxystilbene; 4,4′-dihydroxy-alpha-cyanostilbene;1,1-bis(4-hydroxyphenyl)cyclohexane; 1,4-dihydroxy-3,6-dimethylbenzene;1,4-dihydroxy-3,6-dimethoxybenzene; 1,4-dihydroxy-2-tert-butylbenzene;1,4-dihydroxy-2-bromo-5-methylbenzene; 1,3-dihydroxy-4-nitrophenol;1,3-dihydroxy-4-cyanophenol; tris(hydroxyphenyl)methane,dicyclopentadiene or an oligomer thereof and phenol or substitutedphenol condensation products, and any mixture thereof.

Examples of the di- and polycarboxylic acids (b) include terephthalicacid, isophthalic acid, dicyclopentadienedicarboxylic acid,tris(carboxyphenyl)methane, 4,4′-dicarboxydiphenylmethane;1,4-cyclohexanedicarboxylic acid; 1,6-hexanedicarboxylic acid;1,4-butanedicarboxylic acid; 1,1-bis(4-carboxyphenyl)cyclohexane;3,3′,5,5′-tetra-methyl-4,4′-dicarboxydiphenyl;4,4′-dicarboxy-alpha-methylstilbene;1,4-bis(4-carboxy-phenyl)-trans-cyclohexane;1,1′-bis(4-carboxyphenyl)cyclohexane; 1,3-dicarboxy-4-methylbenzene;1,3-dicarboxy-4-methoxybenzene; 1,3-dicarboxy-4-bromobenzene; and anycombination thereof.

Examples of the di- and polymercaptans (c) include 1,3-benzenedithiol;1,4-benzenedithiol; 4,4′-dimercaptodiphenylmethane;4,4′-dimercaptodiphenyl oxide; 4,4′-dimercapto-alpha-methylstilbene;3,3′,5,5′-tetramethyl-4,4′-dimercaptodiphenyl; 1,4-cyclohexanedithiol;1,6-hexanedithiol; 2,2′-dimercaptodiethylether;1,1-bis(4-mercapto-phenyl)cyclohexane; 1,2-dimercaptopropane,bis(2-mercaptoethyl)sulfide, tris(mercapto-phenyl)methane, and anycombination thereof.

Examples of the di- and polyamines (d) include 1,2-diaminobenzene;1,3-diaminobenzene; 1,4-diaminobenzene; 4,4′-diaminodiphenylmethane;4,4′-diaminodiphenylsulfone; 2,2′-diaminodiphenylsulfone;4,4′-diaminodiphenyl oxide; 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenyl;3,3′-dimethyl-4,4′-diaminodiphenyl; 4,4′-diamino-alpha-methylstilbene;4,4′-diaminobenzanilide; 4,4′-diaminostilbene;1,4-bis(4-aminophenyl)-trans-cyclohexane;1,1-bis(4-aminophenyl)cyclohexane; 1,2-cyclohexanediamine;1,4-bis(aminocyclohexyl)methane; 1,3-bis(aminomethyl)cyclohexane;1,4-bis(aminomethyl)cyclohexane; 1,4-cyclohexanediamine;1,6-hexanediamine; 2,2′-bis(4-aminocyclohexyl)propane;4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine (menthane diamine);piperazine, ethylenediamine, diethyletriamine, triethylenetetramine,tetraethylenepentamine, 1-(2-aminoethyl)piperazine,bis(aminopropyl)ether, bis(aminopropyl)sulfide,bis(aminomethyl)norbornane, isophoronediamine, 1,3-xylenediamine,tris(aminophenyl)methane, and any combination thereof.

Examples of the primary monoamines (e) include ammonia, aniline,4-chloroaniline, 4-methylaniline, 4-methoxyaniline, 4-cyanoaniline,4-aminodiphenyl oxide, 4-aminodiphenylmethane, 4-aminodiphenylsulfide,4-aminobenzophenone, 4-aminodiphenyl, 4-aminostilbene,4-amino-alpha-methylstilbene, methylamine, 4-amino-4′-nitrostilbene,n-hexylamine, cyclohexylamine, aminonorbornane,N,N-diethyltrimethylenediamine; 2,6-dimethylaniline; and any combinationthereof.

Examples of the sulfonamides (f) include phenylsulfonamide,4-methoxyphenylsulfonamide, 4-chlorophenylsulfonamide,4-bromophenylsulfonamide, 4-methylsulfonamide, 4-cyanosulfonamide,4-sulfonamidodiphenyl oxide, 4-sulfonamidodiphenylmethane,4-sulfonamidobenzophenone, 4-sulfonylamidodiphenyl,4-sulfonamidostilbene, 4-sulfonamido-alpha-methylstilbene,2,6-dimethyphenylsulfonamide; and any combination thereof.

Examples of the aminophenols (g) include o-aminophenol, m-aminophenol,p-aminophenol, 2-methoxy-4-hydroxyaniline,3-cyclohexyl-4-hydroxyaniline, 5-butyl-4-hydroxyaniline,3-phenyl-4-hydroxyaniline, 4-(1-(3-aminophenyl)-1-methyl-ethyl)phenol,4-(1-(4-aminophenyl)ethyl)phenol, 4-(4-aminophenoxy)phenol,4-((4-amino-phenyl)thio)phenol,(4-aminophenyl)(4-hydroxyphenyl)methanone,4-((4-amino-phenyl)sulfonyl)phenol, N-methyl-p-aminophenol,4-amino-4′-hydroxy-alpha-methyl-stilbene,4-hydroxy-4′-amino-alpha-methylstilbene,4-(1-(4-amino-3,5-dibromophenyl)-1-methylethyl)-2,6-dibromophenol;3,5-dimethyl-4-hydroxyaniline; 2,6-dibromo-4-hydroxy-aniline; and anycombination thereof.

Examples of the aminocarboxylic acids (h) include 2-aminobenzoic acid,3-aminobenzoic acid, 4-aminobenzoic acid, 2-methoxy-4-aminobenzoic acid,3-cyclohexyl-4-aminobenzoic acid, 5-butyl-4-aminobenzoic acid,3-phenyl-4-aminobenzoic acid, 4-(1-(3-aminophenyl)-1-methylethyl)benzoicacid, 4-(1-(4-aminophenyl)ethyl)benzoic acid, 4-(4-aminophenoxy)benzoicacid, 4-((4-aminophenyl)thio)benzoic acid,(4-aminophenyl)(4-carboxyphenyl)methanone,4-((4-aminophenyl)sulfonyl)benzoic acid, N-methyl-4-aminobenzoic acid,4-amino-4′-carboxy-alpha-methylstilbene,4-carboxy-4′-amino-alpha-methylstilbene, glycine, N-methylglycine,4-aminocyclohexanecarboxylic acid, 4-aminohexanoic acid,4-piperidinecarboxylic acid, 5-aminophthalic acid,4-(1-(4-amino-3,5-dibromophenyl)-1-methylethyl)-2,6-dibromobenzoic acid;3,5-dimethyl-4-aminobenzoic acid; 2,6-dibromo-4-aminobenzoic acid; andany combination thereof.

Examples of the carboxylic acids (i) include 2-hydroxybenzoic acid,3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-methoxy-4-hydroxybenzoicacid, 3-cyclohexyl-4-hydroxybenzoic acid, 5-butyl-4-hydroxybenzoic acid,3-phenyl-4-hydroxybenzoic acid,4-(1-(3-hydroxyphenyl)-1-methylethyl)benzoic acid,4-(1-(4-hydroxyphenyl)ethyl)benzoic acid, 4-(4-hydroxyphenoxy)benzoicacid, 4-((4-hydroxyphenyl)thio)benzoic acid,(4-hydroxyphenyl)(4-carboxyphenyl)methanone,4-((4-hydroxyphenyl)sulfonyl)benzoic acid,4-hydroxy-4′-carboxy-alpha-methylstilbene,4-carboxy-4′-hydroxy-alpha-methylstilbene, 2-hydroxyphenylacetic acid,3-hydroxyphenylacetic acid, 4-hydroxyphenylacetic acid,4-hydroxyphenyl-2-cyclo-hexanecarboxylic acid,4-hydroxyphenoxy-2-propanoic acid, 3,5-dimethyl-4-hydroxybenzoic acid;2,6-dibromo-4-hydroxybenzoic acid;4-(1-(4-hydroxy-3,5-dibromophenyl)-1-methylethyl)-2,6-dibromobenzoicacid; and any combination thereof.

Examples of the sulfanilamides (j) include o-sulfanilamide,m-sulfanilamide, p-sulfanilamide, 2-methoxy-4-aminobenzoic acid,3-methyl-4-sulfonamido-1-aminobenzene,5-methyl-3-sulfonamido-1-aminobenzene,3-phenyl-4-sulfonamido-1-aminobenzene,4-(1-(3-sulfonamidophenyl)-1-methylethyl)aniline,4-(1-(4-sulfonamidophenyl)ethyl)aniline,4-(4-sulfonamidophenoxy)aniline, 4-((4-sulfonamidophenyl)thio)aniline,(4-sulfonamidophenyl)(4-aminophenyl)methanone,4-((4-sulfonamidophenyl)sulfonyl)aniline,4-sulfonamido-1-N-methylaminobenzene,4-amino-4′-sulfonamido-alpha-methylstilbene,4-sulfonamido-4′-amino-alpha-methyl-stilbene,2,6-dimethyl-4-sulfonamido-1-aminobenzene;4-(1-(4-sulfonamido-3,5-dibromo-phenyl)-1-methylethyl)-2,6-dibromoaniline;and any combination thereof.

Particularly preferred examples of the curing catalyst include borontrifluoride, boron trifluoride etherate, aluminum chloride, ferricchloride, zinc chloride, silicon tetrachloride, stannic chloride,titanium tetrachloride, antimony trichloride, boron trifluoridemonoethanolamine complex, boron trifluoride triethanolamine complex,boron trifluoride piperidine complex, pyridine-borane complex,diethanolamine borate, zinc fluoroborate, metallic acylates such asstannous octoate or zinc octoate, and any combination thereof.

The curing catalyst may be employed in an amount which will effectivelythermoset the curable epoxy resin composition or assist in thethermosetting of the thermosettable epoxy resin composition. The amountof the curing catalyst will also depend upon the particularre-epoxidized PACE resin, the curing agent, if any, and epoxy resinother than the PACE resin, if any, employed in the thermosettable epoxyresin composition.

Generally, the curing catalyst may be used in an amount of from about0.001 wt % to about 2 wt %, based on the weight of the totalthermosettable epoxy resin composition. In addition, one or more of thecuring catalysts may be employed to accelerate or otherwise modify thecuring process of the curable epoxy resin composition.

The epoxy resin which can optionally be used as the epoxy resin (c)other than the re-epoxidized PACE resin (a) may be any epoxidecontaining compound which has an average of more than one epoxide groupper molecule. The epoxide group can be attached to any oxygen, sulfur ornitrogen atom or the single bonded oxygen atom attached to the carbonatom of a —CO—O— group. The oxygen, sulfur, nitrogen atom, or the carbonatom of the —CO—O— group may be attached to an aliphatic,cycloaliphatic, polycycloaliphatic or aromatic hydrocarbon group. Thealiphatic, cycloaliphatic, polycycloaliphatic or aromatic hydrocarbongroup can be substituted with any inert substituents including, but notlimited to, halogen atoms, preferably fluorine, bromine or chlorine;nitro groups; or the groups can be attached to the terminal carbon atomsof a compound containing an average of more than one—(O—CHR^(a)—CHR^(a))_(t)— group, wherein each R^(a) is independently ahydrogen atom or an alkyl or haloalkyl group containing from one to twocarbon atoms, with the proviso that only one R^(a) group can be ahaloalkyl group, and t has a value from one to about 100, preferablyfrom one to about 20, more preferably from one to about 10, and mostpreferably from one to about 5.

More specific examples of the epoxy resin which can be used as the epoxyresin (c) include diglycidyl ethers of 1,2-dihydroxybenzene (catechol);1,3-dihydroxybenzene (resorcinol); 1,4-dihydroxybenzene (hydroquinone);4,4′-isopropylidenediphenol (bisphenol A);4,4′-dihydroxydiphenylmethane; 3,3′,5,5′-tetrabromobisphenol A;4,4′-thiodiphenol; 4,4′-sulfonyldiphenol; 2,2′-sulfonyldiphenol;4,4′-dihydroxydiphenyl oxide; 4,4′-dihydroxybenzophenone;1,1′-bis(4-hydroxyphenyl)-1-phenylethane; 3,3′-5,5′-tetrachlorobisphenolA; 3,3′-dimethoxybisphenol A; 4,4′-dihydroxybiphenyl;4,4′-dihydroxy-alpha-methylstilbene; 4,4′-dihydroxybenzanilide;4,4′-dihydroxystilbene; 4,4′-dihydroxy-alpha-cyanostilbene;N,N′-bis(4-hydroxyphenyl)terephthalamide; 4,4′-dihydroxyazobenzene;4,4′-dihydroxy-2,2′-dimethylazoxybenzene;4,4′-dihydroxydiphenylacetylene; 4,4′-dihydroxychalcone; thetetraglycidyl amines of 4,4′-diaminodiphenylmethane;4,4′-diaminostilbene; N,N′-dimethyl-4,4′-diaminostilbene;4,4′-diaminobenzanilide; 4,4′-diaminobiphenyl;4-hydroxyphenyl-4-hydroxybenzoate, dipropylene glycol, poly(propyleneglycol), thiodiglycol, the triglycidyl ether oftris(hydroxyphenyl)methane, the polyglycidyl ethers of a phenol or alkylor halogen substituted phenol-aldehyde acid catalyzed condensationproduct (novolac resins), the polyglycidyl ether of the condensationproduct of a dicyclopentadiene or an oligomer thereof and a phenol oralkyl or halogen substituted phenol, and any combination thereof.

The epoxy resin which can be used as the epoxy resin may also include anadvanced epoxy resin product. The advanced epoxy resin may be a productof an advancement reaction of an epoxy resin with an aromatic di- andpolyhydroxyl, or carboxylic acid containing compound. The epoxy resinused in the advancement reaction may include any one or more of theaforesaid epoxy resins suitable for the epoxy resin comprising the di-or polyglycidyl ethers.

Examples of the aromatic di- and polyhydroxyl or carboxylic acidcontaining compound include 4,4′-dihydroxydiphenylmethane;4,4′-thiodiphenol; 4,4′-sulfonyldiphenol; 2,4-dimethylresorcinol;2,2′-sulfonyldiphenol; 4,4′-dihydroxydiphenyl oxide;4,4′-dihydroxybenzophenone; 1,1-bis(4-hydroxyphenyl)-1-phenylethane;4,4′-bis(4(4-hydroxyphenoxy)-phenylsulfone)diphenyl ether;4,4′-dihydroxydiphenyl disulfide;3,3′,3,5′-tetrachloro-4,4′-isopropylidenediphenol;3,3′,3,5′-tetrabromo-4,4′-isopropylidenediphenol;3,3′-dimethoxy-4,4′-isopropylidene-diphenol; 4,4′-dihydroxybiphenyl;4,4′-dihydroxy-alpha-methylstilbene; 4,4′-dihydroxybenzanilide;bis(4-hydroxyphenyl)terephthalate;N,N′-bis(4-hydroxyphenyl)terephthalamide; 4,4′-dihydroxyphenylbenzoate;bis(4′-hydroxyphenyl)-1,4-benzenediimine;1,1′-bis(4-hydroxyphenyl)cyclohexane;2,2′,5,5′-tetrahydroxydiphenylsulfone;bis(4′-hydroxybiphenyl)terephthalate; 4,4′-benzanilidedicarboxylic acid;4,4′-phenylbenzoatedicarboxylic acid; 4,4′-stilbenedicarboxylic acid,hydroquinone, resorcinol, catechol, 4-chlororesorcinol,tetramethylhydroquinone, bisphenol A, phloroglucinol,pyrogallol,tris(hydroxyphenyl)methane, dicyclopentadiene diphenol,tricyclopentadienediphenol, terephthalic acid, isophthalic acid, adipicacid, and any combination thereof.

Preparation of the aforementioned advanced epoxy resin products can beperformed using known methods, for example, an advancement reaction ofan epoxy resin with one or more suitable compounds having an average ofmore than one reactive hydrogen atom per molecule, wherein the reactivehydrogen atom is reactive with an epoxide group in the epoxy resin.

The ratio of the compound having an average of more than one reactivehydrogen atom per molecule to the epoxy resin is generally from about0.01:1 to about 0.95:1, preferably from about 0.05:1 to about 0.8:1, andmore preferably from about 0.10:1 to about 0.5:1 equivalents of thereactive hydrogen atom per equivalent of the epoxide group in the epoxyresin.

In addition to the aforementioned dihydroxyaromatic and dicarboxylicacid compounds, examples of the compound having an average of more thanone reactive hydrogen atom per molecule may also include dithiol,disulfonamide or compounds containing one primary amine or amide group,two secondary amine groups, one secondary amine group and one phenolichydroxy group, one secondary amine group and one carboxylic acid group,or one phenolic hydroxy group and one carboxylic acid group, and anycombination thereof.

The advancement reaction may be conducted in the presence or absence ofa solvent with the application of heat and mixing. The advancementreaction may be conducted at atmospheric, superatmospheric orsubatmospheric pressures and at temperatures of from about 20° C. toabout 260° C., preferably, from about 80° C. to about 240° C., and morepreferably from about 100° C. to about 200° C.

The time required to complete the advancement reaction depends uponfactors such as the temperature employed, the chemical structure of thecompound having more than one reactive hydrogen atom per moleculeemployed, and the chemical structure of the epoxy resin employed. Highertemperature may require shorter reaction time whereas lower temperaturerequires a longer period of reaction time. In general, the time forcompletion of the advancement reaction may ranged from about 5 minutesto about 24 hours, preferably from about 30 minutes to about 8 hours,and more preferably from about 30 minutes to about 4 hours.

A catalyst may also be added in the advancement reaction. Examples ofthe catalyst may include phosphines, quaternary ammonium compounds,phosphonium compounds and tertiary amines. The catalyst may be employedin quantities of from about 0.01 wt % to about 3 wt %, preferably fromabout 0.03 wt % to about 1.5 wt %, and more preferably from about 0.05wt % to about 1.5 wt %, based upon the total weight of the epoxy resin.

Other details concerning an advancement reaction useful in preparing theadvanced epoxy resin product for the resin are provided in U.S. Pat. No.5,736,620 and in Handbook of Epoxy Resins by Henry Lee and Kris Neville,both of which are incorporated herein by reference.

The thermosettable epoxy resin composition may also be blended with atleast one additive including, for example, a cure accelerator, a solventor diluent, a modifier such as a flow modifier and/or a thickener, areinforcing agent, a filler, a pigment, a dye, a mold release agent, awetting agent, a stabilizer, a fire retardant agent, a surfactant, orany combination thereof.

The additive may be blended with the re-epoxidized PACE resin, thecuring agent, if used, and the epoxy resin other than the re-epoxidizedPACE resin, if used or with any combination thereof prior to use for thepreparation of the thermosettable epoxy resin composition of the presentinvention.

These additives may be added in functionally equivalent amounts, forexample, the pigment and/or dye may be added in quantities which willprovide the composition with the desired color. In general, the amountof the additives may be from about zero wt % to about 20 wt %,preferably from about 0.5 wt % to about 5 wt %, and more preferably fromabout 0.5 wt % to about 3 wt %, based upon the total weight of thethermosettable epoxy resin composition.

The cure accelerator which can be employed herein includes, for example,mono, di, tri and tetraphenols; chlorinated phenols; aliphatic orcycloaliphatic mono or dicarboxylic acids; aromatic carboxylic acids;hydroxybenzoic acids; halogenated salicylic acids; boric acid; aromaticsulfonic acids; imidazoles; tertiary amines; aminoalcohols;aminopyridines; aminophenols; mercaptophenols; and any mixture thereof.

Particularly suitable cure accelerators include 2,4-dimethylphenol,2,6-dimethylphenol, 4-methylphenol, 4-tertiary-butylphenol,2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 4-nitrophenol,1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 2,2′-dihydroxybiphenyl,4,4′-isopropylidenediphenol, valeric acid, oxalic acid, benzoic acid,2,4-dichlorobenzoic acid, 5-chlorosalicylic acid, salicylic acid,p-toluenesulfonic acid, benzenesulfonic acid, hydroxybenzoic acid,4-ethyl-2-methylimidazole, 1-methylimidazole, triethylamine,tributylamine, N,N-diethylethanolamine, N,N-dimethylbenzylamine,2,4,6-tris(dimethylamino)phenol, 4-dimethylaminopyridine, 4-aminophenol,2-aminophenol, 4-mercaptophenol, and any combination thereof.

Examples of the solvent or diluent which can be employed herein include,for example, aliphatic and aromatic hydrocarbons, halogenated aliphatichydrocarbons, aliphatic ethers, aliphatic nitriles, cyclic ethers,glycol ethers, esters, ketones, amides, sulfoxides, and any combinationthereof.

Particularly suitable solvents include pentane, hexane, octane, toluene,xylene, methylethylketone, methylisobutylketone, N,N-dimethylformamide,dimethylsulfoxide, diethyl ether, tetrahydrofuran, 1,4-dioxane,dichloromethane, chloroform, ethylene dichloride, methyl chloroform,ethylene glycol dimethyl ether, diethylene glycol methyl ether,dipropylene glycol methyl ether, N-methylpyrrolidinone,N,N-dimethylacetamide, acetonitrile, sulfolane, and any combinationthereof.

The modifier such as the thickener and the flow modifier may be employedin amounts of from zero wt % to about 10 wt %, preferably, from about0.5 wt % to about 6 wt %, and more preferably from about 0.5 wt % toabout 4 wt %, based upon the total weight of the thermosettable epoxyresin blend composition.

The reinforcing material which may be employed herein includes naturaland synthetic fibers in the form of woven fabric, mat, monofilament,multifilament, unidirectional fiber, roving, random fiber or filament,inorganic filler or whisker, or hollow sphere. Other suitablereinforcing material includes glass, carbon, ceramics, nylon, rayon,cotton, aramid, graphite, polyalkylene terephthalates, polyethylene,polypropylene, polyesters, and any combination thereof.

The filler which may be employed herein includes, for example, inorganicoxide, ceramic microsphere, plastic microsphere, glass microsphere,inorganic whisker, calcium carbonate, and any combination thereof.

The filler may be employed in an amount of from zero wt % to about 95 wt%, preferably from about 10 wt % to about 80 wt %, and more preferablyfrom about 40 wt % to about 60 wt %, based upon the total weight of thethermosettable epoxy resin composition.

Another embodiment of the present invention comprises a partially(B-staged) or a totally cured (thermoset) product from thethermosettable epoxy resin composition described above.

The process of thermosetting the thermosettable epoxy resin compositionof the present invention may be conducted at atmospheric (e.g. 760 mmHg), superatmospheric or subatmospheric pressures and at a temperaturefrom about 0° C. to about 300° C., preferably from about 25° C. to about250° C., and more preferably from about 50° C. to about 200° C.

The time required to complete the curing may depend upon the temperatureemployed. Higher temperatures generally require a shorter period of timewhereas lower temperatures generally require longer periods of time. Ingeneral, the required time for completion of the curing is from about 1minute to about 48 hours, preferably from about 15 minutes to about 24hours, and more preferably from about 30 minutes to about 12 hours. Itis also operable to partially thermoset the thermosettable epoxy resincomposition of the present invention to form a B-stage product andsubsequently cure the B-stage product completely at a later time.

Another embodiment of the present invention comprises an articleprepared from the B-staged (partially thermoset) or the totally cured(thermoset) product described above. The article may include, forexample, coatings, especially protective coatings with excellent solventresistant, moisture resistant, abrasion resistant, impact resistant, andweatherable (e.g., UV resistant, non-chalking) properties; a reactivetoughener for thermosets including epoxy resin based thermosets; can andcoil coatings; maintenance coatings including coatings for stone,concrete and flooring; marine coatings including anti-fouling coatings;powder coatings including both decorative and functional types;automotive coatings; corrosion resistant coatings; electrical orstructural laminates and composites; encapsulations; general castings;coatings for other plastics and metals; sealants; filament windings;moldings; polymer modified concrete; binders; adhesives including windowglass adhesives; paints lacquers, and varnishes. Articles which comprisea fully aliphatic/cycloaliphatic cured epoxy resin (with no aromaticrings) of the present invention are especially desirable for theiroutstanding balance of physical and mechanical properties.

EXAMPLES

The following Examples and Comparative Examples further illustrate thepresent invention in detail but are not to be construed to limit thescope thereof.

The following standard abbreviations are used in the Examples andComparative Examples: “GC” stands for gas chromatography(chromatographic); “MS” stands for mass spectrometry (spectrometric);“DSC” stands for differential scanning calorimetry; “Tg” stands forglass transition temperature(s); “EEW” stands for epoxide equivalentweight; “AHEW” stands for amine hydrogen equivalent weight; “DI” standsfor deionized; “meq” stands for milliequivalent(s); “eq” stands forequivalent(s); “wt” stands for weight(s); “min” stands for minute(s);“hr” stands for hour(s); “g” stands for gram(s); “mL” stands formilliliter(s); “L” stands for liter(s); “LPM” stands for liter(s) perminute; “μm” stands for micrometer(s); “mm” stands for millimeter(s);“m” stands for meter(s); “cp” stands for centipoise; “J” stands forjoule(s); and “DETA” stands for diethylenetriamine.

In the following Examples and Comparative Examples, standard analyticalequipment and methods are used such as for example, the following:

Gas Chromatogaphic Analysis: Area %

In the general method, a Hewlett Packard 5890 Series II Plus gaschromatograph was employed using a DB-1 capillary column (61.4 m by 0.25mm with a 0.25 μm film thickness, Agilent). The column was maintained inthe chromatograph oven at a 50° C. initial temperature. Both theinjector inlet and flame ionization detector were maintained at 300° C.Helium carrier gas flow through the column was maintained at 1.1 mL permin. For the analyses of the epoxy resins during synthesis or from therotary evaporation, an initial 50° C. oven temperature with heating at12° C. per min to a final temperature of 300° C. revealed thatessentially all light boiling components, including residualepichlorohydrin, cyclohexanedimethanols and monoglycidyl ethers of thecyclohexanedimethanols had been removed by the rotary evaporation. Forthe analyses of the PACE resins and re-epoxidized PACE resins, aninitial 250° C. oven temperature with heating at 13.3° C. per min to afinal temperature of 300° C. was employed for complete elution of alloligomeric components within 50 min total time for the analysis. GCanalyses in area %, are not a quantitative measure of any givencomponent.

Samples for GC analysis were prepared by collection of a 0.5 mL aliquotof the slurry product from the epoxidation and addition to a vialcontaining 1 mL of acetonitrile. After shaking to mix, a portion of theslurry in acetonitrile was loaded into a 1 mL syringe (Norm-Ject, allpolypropylene/polyethylene, Henke Sass Wolf GmBH) and passed through asyringe filter (Acrodisc CR 13 with 0.2 μm PTFE membrane, PallCorporation, Gelman Laboratories) to remove any insoluble debris.

Internally Standardized Gas Chromatographic Analysis for Weight PercentResidual Diglycidyl Ethers of cis-, trans-1,3- and1,4-Cyclohexanedimethanol in the Polyfunctional Cycloaliphatic EpoxyResin and Re-Epoxidized Polyfunctional Cycloaliphatic Epoxy Resin

A single point internal standard method was developed for gaschromatographic analysis of residual diglycidyl ethers of cis-,trans-1,3- and 1,4-cyclohexanedimethanol remaining in the PACE resin(distillation pot) product and the re-epoxidized PACE resin.Cyclohexanone was selected as the internal standard since it had aretention time that was different from that of any other componentsobserved in the analyses of the epoxidation products. For the standardof the diglycidyl ether of cis-, trans-1,3- and1,4-cyclohexanedimethanol, a distillation cut was employed. Thisdistillation cut contained 0.71 wt % monoglycidyl ethers and 99.29 wt %diglycidyl ethers. A 0.2500 g sample of the standard of the diglycidylethers plus 0.7500 g of acetonitrile plus 5 μL of cyclohexanone weighing0.0047 g. were added to a glass vial. Three separate injections weremade in the gas chromatograph and the resultant area counts wereaveraged for the cyclohexanone and for the diglycidyl ether. This datawas used to calculate the internal response factor, as follows:

${{Internal}\mspace{14mu} {Response}\mspace{14mu} {Factor}} = {\frac{\left( {{area}\mspace{14mu} {internal}\mspace{14mu} {standard}} \right)\left( {{amount}\mspace{14mu} {diglycidyl}\mspace{14mu} {ethers}} \right)}{\left( {{amount}\mspace{14mu} {internal}\mspace{14mu} {standard}} \right)\left( {{area}\mspace{14mu} {diglycidyl}\mspace{14mu} {ethers}} \right)} =}$

An aliquot (0.2500 g) of the PACE resin from Comparative Example A,acetonitrile (0.7500 g) and cyclohexanone (5 μL, 0.0042 g) were added toa glass vial and analyzed by GC. Using the data from the GC analysisplus the internal response factor, the following calculation wasperformed:

${\% \mspace{14mu} {Epoxide}} = \frac{\left\lbrack {\left( {{mL}\mspace{14mu} {titrated}\mspace{14mu} {sample}} \right) - \left( {{mL}\mspace{14mu} {titrated}\mspace{14mu} {blank}} \right)} \right\rbrack (0.4303)}{\left( {g\mspace{14mu} {sample}\mspace{14mu} {titrated}} \right)}$${EEW} = \frac{4303}{\% \mspace{14mu} {epoxide}}$

I.C.I. Cone and Plate Viscosity

Viscosity was determined on an I.C.I. Cone and Plate ViscometerViscosity (model VR-4540) at 25° C. In the method, the viscometerequipped with a 0-40 poise spindle (model VR-4140) and equilibrated to25° C. was calibrated to zero then the sample applied and held 2 minwith viscosity then checked and the reading taken after 15 seconds. Oneor more duplicate viscosity tests were completed using a fresh aliquotof the particular product being tested. The individual measurements wereaveraged.

Percent Epoxide/Epoxide Equivalent Weight Analysis

A standard titration method was used to determine percent epoxide in thevarious epoxy resins [Jay, R. R., “Direct Titration of Epoxy Compoundsand Aziridines”, Analytical Chemistry, 36, 3, 667-668 (March, 1964).] Inthe present adaptation of this method, the carefully weighed sample(sample weight ranges from 0.17-0.18 g) was dissolved in dichloromethane(15 mL) followed by the addition of tetraethylammonium bromide solutionin acetic acid (15 mL). The resultant solution treated with 3 drops ofcrystal violet indicator (0.1% w/v in acetic acid) was titrated with0.1N perchloric acid in acetic acid on a Metrohm 665 Dosimat titrator(Brinkmann). Titration of a blank consisting of dichloromethane (15 mL)and tetraethylammonium bromide solution in acetic acid (15 mL) providedcorrection for solvent background. Percent epoxide and EEW werecalculated using the following equations:

${{Amount}\mspace{14mu} {Diglycidyl}\mspace{14mu} {Ethers}} = \frac{\begin{matrix}\left( {{amount}\mspace{14mu} {internal}\mspace{14mu} {standard}} \right) \\{\left( {{area}\mspace{14mu} {diglycidyl}\mspace{14mu} {ethers}} \right)\left( {{Internal}\mspace{14mu} {Response}\mspace{14mu} {Factor}} \right)}\end{matrix}}{\left( {{area}\mspace{14mu} {internal}\mspace{14mu} {standard}} \right)}$

Differential Scanning Calorimetry (DSC)

For analysis of (1) curing of the thermosettable blend of the PACE resinor re-epoxidized PACE resin with DETA and of the (2) Tg of a curedsample a DSC 2910 Modulated DSC (TA Instruments) was employed, using aheating rate of 7° C. per min from 0° C. to 300° C. under a stream ofnitrogen flowing at 35 cubic centimeters per min. Each sample wascontained in an aluminum pan and loosely covered (not sealed) with analuminum lid. The respective sample weight tested is given with theresults obtained.

For analysis of curing of the thermosettable blend of the diglycidylether of UNOXOL™ Diol (cis-, trans-1,3- and 1,4-cyclohexanedimethanol)cured with DETA and the Tg of the thermoset thereof, the aforementionedconditions were employed, but with an end temperature of 250° C.

Comparative Example A Three Stage Synthesis of Epoxy Resin of UNOXOL™Diol with Postreaction Temperature Held at 40° C.

Epoxidation of UNOXOL™ Diol was performed using three stages of aqueoussodium hydroxide addition with postreaction at 40° C. followed byfractional vacuum distillation to separate the constituents of the epoxyresin:

A. Epoxidation Reaction

A 5 L, 4 neck, glass, round bottom reactor was charged with UNOXOL™ Diol(432.63 g, 3.0 moles, 6.0 hydroxyl eq), epichlorohydrin (1110.24 g, 12.0moles, 2:1 epichlorohydrin:UNOXOL™ Diol hydroxyl eq ratio), toluene (2.5L), and benzyltriethylammonium chloride (43.62 g, 0.1915 mole) in theindicated order. [UNOXOL™ cyclic dialcohol is a registered trademark ofthe Union Carbide Corporation.] The reactor was additionally equippedwith a condenser (maintained at 0° C.), a thermometer, a_Claisenadaptor, an overhead nitrogen inlet (1 LPM N₂ used), and a stirrerassembly (Teflon™ paddle, glass shaft, variable speed motor). [Teflon™fluorocarbon resin is a trademark of E.I. duPont de Nemours.] Acontroller monitored the temperature registered on the thermometer inthe reactor and provided heating via the heating mantle placed under thereactor as well as cooling delivered by a pair of fans positioned on thereactor exterior. Sodium hydroxide (360.0 g, 9.0 moles) dissolved in DIwater (360 g) for the initial addition was added to a side arm ventedaddition funnel, sealed with a ground glass stopper, then attached tothe reactor. Stirring commenced to give a 22.5° C. mixture followed bycommencement of dropwise addition of the aqueous sodium hydroxidesolution. The reaction mixture was allowed to self-heat to 40° C. duringthe aqueous sodium hydroxide addition time and then held at thattemperature via cooling from the fans as needed. Thus, after 196 min thereaction temperature first reached 40° C. and then remained at 39-40° C.for the remainder of the aqueous sodium hydroxide addition. Addition ofthe aqueous sodium hydroxide required a total of 233 min. Fourteen minafter completion of the aqueous sodium hydroxide addition, heatingcommenced to maintain the reaction at 40° C. After 16.2 hr ofpostreaction at 40° C., stirring ceased, and the reactor contents wereallowed to settle. The organic layer was decanted from the reactorfollowed by addition of 1.5 L of DI water to the salt and residualtoluene left behind in the reactor. After addition into a 2 L separatoryfunnel and settling, the toluene layer which separated from the aqueoussalt solution was recovered and combined back with the decanted organiclayer. The aqueous layer was discarded as waste. GC analysis afternormalization to remove solvents (acetonitrile and toluene) andunreacted epichlorohydrin revealed the presence of 2.21 area % lightcomponents, 1.27 area % unreacted cis-, trans-1,3- and1,4-cyclohexanedimethanol; 43.13 area % monoglycidyl ethers, 0.25 area %of a pair of components associated with the diglycidyl ether peaks,50.20 area % diglycidyl ethers, and 2.94 area % oligomers that werevolatile under the conditions of the GC analysis.

The organic layer was reloaded into the reactor along with freshbenzyltriethylammonium chloride (21.81 g, 0.0958 mole). Sodium hydroxide(180 g, 4.5 moles) dissolved in DI water (180 g) was added to a side armvented addition funnel, sealed with a ground glass stopper, thenattached to the reactor. Stirring commenced to give a 23.5° C. mixturefollowed by commencement of dropwise addition of the aqueous sodiumhydroxide solution. The reaction mixture was allowed to self-heat duringthe aqueous sodium hydroxide addition time. Thus, after 119 min 100% ofthe aqueous sodium hydroxide was added causing the reaction temperatureto reach a maximum of 30.5° C. Three min after completion of the aqueoussodium hydroxide addition, heating commenced to bring the reaction to40° C. after 11 min of heating. After 15.8 hr of postreaction at 40° C.,stirring ceased, and the reactor contents were allowed to settle. Theorganic layer was decanted from the reactor followed by addition of 1.0L of DI water to the salt and residual toluene left behind in thereactor. After addition into a 2 L separatory funnel and settling, thetoluene layer which separated from the aqueous salt solution wasrecovered and combined back with the decanted organic layer. The aqueouslayer was discarded as waste. GC analysis after normalization to removesolvents (acetonitrile and toluene) and unreacted epichlorohydrinrevealed the presence of 5.62 area % light components, no detectableunreacted cis-, trans-1,3- and 1,4-cyclohexanedimethanol; 12.63 area %monoglycidyl ethers, 0.64 area % of a pair of components associated withthe diglycidyl ether peaks, 76.30 area % diglycidyl ethers, and 4.81area % oligomers that were volatile under the conditions of the GCanalysis.

The organic layer was reloaded into the reactor along with freshbenzyltriethylammonium chloride (10.91 g, 0.0479 mole). Sodium hydroxide(90 g, 2.25 moles) dissolved in DI water (90 g) was added to a side armvented addition funnel, sealed with a ground glass stopper, thenattached to the reactor. Stirring commenced to give a 23° C. mixturefollowed by commencement of dropwise addition of the aqueous sodiumhydroxide solution. The reaction mixture was allowed to self-heat duringthe aqueous sodium hydroxide addition time. Thus, after 50 min 66.67% ofthe aqueous sodium hydroxide was added causing the reaction temperatureto reach a maximum of 24.5° C. This temperature was maintained for theremainder of the aqueous sodium hydroxide addition. Addition of theaqueous sodium hydroxide required a total of 61 min Immediately aftercompletion of the aqueous sodium hydroxide addition, heating commencedto bring the reaction to 40° C. after 22 min of heating. After 16.7 hrof postreaction at 40° C., stirring ceased, and the reactor contentswere allowed to settle. The organic layer was decanted from the reactorfollowed by addition of 1.0 L of DI water to the salt and residualtoluene left behind in the reactor. After addition into a 2 L separatoryfunnel and settling, the toluene layer which separated from the aqueoussalt solution was recovered and combined back with the decanted organiclayer. The aqueous layer was discarded as waste. GC analysis afternormalization to remove solvents (acetonitrile and toluene) andunreacted epichlorohydrin revealed the presence of 8.62 area % lightcomponents, no detectable unreacted cis-, trans-1,3- and1,4-cyclohexanedimethanol; 9.91 area % monoglycidyl ethers, 0.46 area %of a pair of components associated with the diglycidyl ether peaks,75.29 area % diglycidyl ethers, and 5.72 area % oligomers that werevolatile under the conditions of the GC analysis.

B. Epoxy Resin Product Isolation

After removal of the aqueous layer from the reaction with the thirdaqueous sodium hydroxide addition, the organic layer was equally splitbetween the pair of separatory funnels and the contents of eachrespective separatory funnel then washed with DI water (400 mL) byvigorously shaking. The washed product was allowed to settle for 2 hoursand then the aqueous layer was removed and discarded as waste. A secondwash was completed using the aforementioned method, with settlingovernight (20 hr) required to fully resolve the organic and aqueouslayers. The combined, hazy organic solution was filtered through a bedof anhydrous, granular sodium sulfate in a 600 mL fritted glass funnelproviding a transparent filtrate.

Rotary evaporation of the filtrate using a maximum oil bath temperatureof 100° C. to a final vacuum of 2.4 mm of Hg removed the bulk of thevolatiles. A total of 712.20 g of light yellow colored, transparentliquid was recovered after completion of the rotary evaporation. GCanalysis after normalization to remove solvent (acetonitrile) revealedthe presence of 9.76 area % monoglycidyl ethers, 0.38 area % of a pairof components associated with the diglycidyl ether peaks, 82.39 area %diglycidyl ethers, and 7.47 area % oligomers that were volatile underthe conditions of the GC analysis. Thus, GC analysis revealed thatessentially all light boiling components, including residualepichlorohydrin, had been removed.

C. Fractional Vacuum Distillation

A portion (699.19 g) of the product from the rotary evaporation wasadded to a 1 L, 3 neck, glass, round bottom reactor equipped withmagnetic stirring and a thermometer for monitoring the pot temperature.A one piece integral vacuum jacketed Vigreux distillation column withdistillation head was used. The distillation column nominally provided 9to 18 theoretical plates depending on the mode of operation. A secondsection of jacketed Vigreux distillation column was added between theone piece integral vacuum jacketed Vigreux distillation column with headand the reactor to provide an additional 9 to 18 theoretical plates. Thedistillation head was equipped with an overhead thermometer, air cooledcondenser, a receiver and a vacuum takeoff. A vacuum pump was employedalong with a liquid nitrogen trap and an in-line digital thermalconductivity vacuum gauge. Stirring commenced followed by application offull vacuum then progressively increased heating using athermostatically controlled heating mantle. A clean receiver was used tocollect each respective distillation cut. During the distillation, theinitial distillation cuts were taken to sequentially remove allcomponents boiling below the cyclohexanedimethanols, all unreactedcyclohexanedimethanols, and the bulk of the monoglycidyl ethers. Thefinal distillation cuts sought to selectively remove diglycidyl ether,leaving the oligomeric product (279.39 g) in the distillation pot. GCanalysis using a cyclohexanone internal standard revealed that theoligomers contained residual 13.91 wt % diglycidyl ether with thebalance as the oligomers. After normalization to remove the peaksassociated with acetonitrile solvent and the diglycidyl ether, the GCanalysis demonstrated the following oligomeric components containingmultiple isomers:

-   2.54 area % 2-propanol, 1-(oxiranylmethoxy)-3-[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-    -   and-   oxirane, 2-[[2-chloro-1-[[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]--   27.80 area % oxirane, 2-[[[3(or    4)-[[2,3-bis(oxiranylmethoxy)propoxy]methyl]cyclohexyl]methoxy]methyl]--   15.91 area % 2-propanol, 1,3-bis[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]--   53.74 area % oxirane, 2-[[2-[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-1-[[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]-    Titration demonstrated an EEW of 193.62. I.C.I. cone and plate    viscosity was 3268 cp.

Example 1 Synthesis of Re-Epoxidized Polyfunctional CycloaliphaticOligomeric Epoxy Resin

Re-epoxidation of the polyfunctional cycloaliphatic oligomer product(Comparative Example A) was performed using two stages of aqueous sodiumhydroxide addition:

A. Re-Epoxidation Reaction

A 5 L, 4 neck, glass, round bottom reactor was charged withpolyfunctional cycloaliphatic oligomer product (250.0 g),epichlorohydrin (277.7 g, 3.0 moles), toluene (1.0 L) andbenzyltriethylammonium chloride (10.91 g, 0.0479 mole). The reactor wasadditionally equipped as specified above (Comparative Example A). Thepolyfunctional cycloaliphatic oligomer product used came fromComparative Example A, C. Fractional Vacuum Distillation. Sodiumhydroxide (90.0 g, 2.25 moles) dissolved in DI water (90 g) for theinitial addition was added to a side arm vented addition funnel, sealedwith a ground glass stopper, then attached to the reactor. Stirringcommenced to give a 23° C. mixture followed by commencement of dropwiseaddition of the aqueous sodium hydroxide solution. The reaction mixturewas allowed to self-heat to 25° C. during the aqueous sodium hydroxideaddition. Thus, after 67 min the reaction temperature first reached 25°C. and then remained at 25° C. for the remainder of the aqueous sodiumhydroxide addition. Addition of the aqueous sodium hydroxide required atotal of 75 min. One min after completion of the aqueous sodiumhydroxide addition, heating commenced to bring the reaction to 40° C.after 22 min of heating. After 21.0 hr of postreaction at 40° C.,stirring ceased, and the reactor contents were allowed to settle. Theorganic layer was decanted from the reactor and processed as specifiedabove (Comparative Example A).

The organic layer was reloaded into the reactor along with freshbenzyltriethylammonium chloride (10.91 g, 0.0479 mole). Sodium hydroxide(90.0 g, 2.25 moles) dissolved in DI water (90 g) was added to a sidearm vented addition funnel, sealed with a ground glass stopper, thenattached to the reactor. Stirring commenced to give a 24° C. mixturefollowed by commencement of dropwise addition of the aqueous sodiumhydroxide solution. The reaction mixture was allowed to self-heat duringthe aqueous sodium hydroxide addition time. Thus, after 43 min thereaction temperature first reached 25° C. and then remained at 25° C.for the remainder of the aqueous sodium hydroxide addition. Addition ofthe aqueous sodium hydroxide required a total of 62 min Immediatelyafter completion of the aqueous sodium hydroxide addition, heatingcommenced to bring the reaction to 40° C. after 28 min of heating. After16.7 hr of postreaction at 40° C., stirring ceased, and the reactorcontents were allowed to settle. The organic layer was decanted from thereactor and processed as specified above (Comparative Example A).

B. Epoxy Resin Product Isolation

The organic layer from the reaction was processed as specified above(Comparative Example A). Rotary evaporation of the filtrate using amaximum oil bath temperature of 100° C. to a final vacuum of 2.7 mm ofHg removed the bulk of the volatiles. A total of 251.14 g of light ambercolored, transparent liquid was recovered after completion of the rotaryevaporation. GC analysis using a cyclohexanone internal standardrevealed that the oligomers contained residual 10.34 wt % diglycidylether with the balance as the oligomers. After normalization to removethe peaks associated with acetonitrile solvent and the diglycidyl ether,the GC analysis demonstrated the following oligomeric components:

-   0.95 area % 2-propanol, 1-(oxiranylmethoxy)-3-[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-    -   and-   oxirane, 2-[[2-chloro-1-[[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]--   28.56 area % oxirane, 2-[[[3(or    4)-[[2,3-bis(oxiranylmethoxy)propoxy]methyl]cyclohexyl]methoxy]methyl]--   70.49 area % oxirane, 2-[[2-[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-1-[[[3(or    4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]-    Titration demonstrated an EEW of 181.6. I.C.I. cone and plate    viscosity was 2972 cp.

Example 2 Preparation and Curing of Thermosettable Blend ofRe-Epoxidized Polyfunctional Oligomeric Epoxy Resin andDiethylenetriamine

A portion (11.3141 g, 0.062299 epoxide equivalent) of the re-epoxidizedPACE resin from Example 1 and DETA (1.289 g, 0.06247 N—H eq) were addedto a glass bottle and vigorously stirred together. A portion (11.2 mg)of the homogeneous solution was removed for DSC analysis. An exothermattributed to curing was observed with a 49.4° C. onset, 119.6° C.maximum, and a 202.94° C. endpoint accompanied by an enthalpy of 466.9J/g.

Comparative Example B Preparation and Curing of Thermosettable Blend ofPolyfunctional Oligomeric Epoxy Resin Reactant and Diethylenetriamine

A portion (11.2483 g, 0.058094 epoxide equivalent) of the PACE resinfrom Comparative Example A and DETA (1.200 g, 0.058156 N—H equivalent)were added to a glass bottle and vigorously stirred together. A portion(12.0 mg) of the homogeneous solution was removed for DSC analysis. Anexotherm attributed to curing was observed with a 51.9° C. onset, 113.6°C. maximum, and a 212.89° C. endpoint accompanied by an enthalpy of424.2 J/g.

Example 3 Preparation of Clear, Unfilled Casting of Thermosettable Blendof Re-Epoxidized Polyfunctional Oligomeric Epoxy Resin andDiethylenetriamine and Analysis of Glass Transition Temperature

The remaining portion of the re-epoxidized PACE resin and DETA blendfrom Example 2 was added to an aluminum dish (2.5 inch diameter by 0.5inch deep) and cured in an oven using the following schedule: 1 hour at70° C., 1 hour at 100° C., 1 hour at 125° C., 1 hour at 150° C. and 1hour at 200° C. A portion (20.8 mg) of the transparent, light ambercolored casting was removed for DSC analysis. A Tg of 67.2° C. wasobserved, with no indication of further curing or exothermicdecomposition observed up to the 300° C. DSC analysis temperature. Asecond scanning using the aforementioned conditions again revealed a67.0° C. Tg.

Comparative Example C Preparation of Clear, Unfilled Casting ofThermosettable Blend of Polyfunctional Oligomeric Epoxy Resin Reactantand Diethylenetriamine and Analysis of Glass Transition Temperature

The remaining portion of the PACE resin and DETA blend from ComparativeExample B was added to an aluminum dish and cured using the method ofExample 3. A portion (26.0 mg) of the transparent, light amber coloredcasting was removed for DSC analysis using a temperature range of 0° C.to 300° C. A Tg of 59.0° C. was observed, with no indication of furthercuring or exothermic decomposition observed up to the 300° C. DSCanalysis temperature. A second scanning using the aforementionedconditions again revealed a 57.4° C. Tg.

Comparative Example D Curing of High Purity Diglycidyl Ether of cis-,trans-1,3- and 1,4-Cyclohexanedimethanol with DETA

A portion (5.0226 g, 0.03900 epoxide equivalent) of diglycidyl ether ofUNOXOL™ Diol (cis-, trans-1,3- and 1,4-cyclohexanedimethanol) obtainedfrom the fractional vacuum distillation of the epoxy resin of UNOXOL™Diol from a three stage synthesis was added to a glass vial. G.C.analysis of the diglycidyl ether demonstrated 99.49 wt % diglycidylethers, 0.16 wt % monoglycidyl ethers, 0.35 wt. % of a pair of minorpeaks associated with the diglycidyl ether peak and no detectableoligomers. DETA (0.81 g, 0.03926 amine hydrogen eq) was added to theglass vial then the contents were vigorously stirred together to give ahomogeneous mixture. DSC analysis was completed using a 11.4 mg portionof the solution. An exothermic transition, attributable to reaction ofthe reactive hydrogen atoms in the curing agent with the epoxide groups,was observed with an onset temperature of 44.9° C., a maximum at 116.8°C., an enthalpy of 719.7 J/g, and an end temperature of 203.8° C. Thecured product recovered from the DSC analysis was a transparent, lightyellow colored, rigid solid.

Comparative Example E Preparation of a Clear, Unfilled Casting of HighPurity Diglycidyl Ether of cis-, trans-1,3- and1,4-Cyclohexanedimethanol Cured with DETA and Analysis of GlassTransition Temperature

The remaining portion of the curable mixture from Comparative Example Dwas added to an aluminum dish and then placed in an oven and cured usingthe method of Example 3. The cured product was a rigid, light ambercolored, transparent solid. Portions (28.5 and 32.4 mg) of the curedproduct were tested by DSC analysis using the method previously given(end temperature was 250° C.). The casting obtained from curingdiglycidyl ether of cis-, trans-1,3- and 1,4-cyclohexanedimethanol withDETA exhibited regions of deep channels or cracks which were firstobserved during the initial curing at 70° C. It is possible that thevery high enthalpy on curing (Comparative Example D) may be responsiblefor the channels propagated through the casting. Two separate samples ofthe casting were randomly taken and for the DSC analyses (Tables I andII). In the DSC analyses of both Samples 1 and 2, residual exothermicitywas present in the first scanning and indicated incomplete cure. Uponsecond scanning the residual exothermicity was no longer detected inSample 2, but was still present Sample 1 but in a reduced amount. Thelarge enthalpy associated with this curable mixture (Comparative ExampleD) may be responsible for the incomplete cure, with cure occurring soenergetically that the mobility of amine groups and epoxide groups inthe thermosetting matrix is restricted.

TABLE I Glass Transition Temperature for Diglycidyl Ether of cis-,trans-1,3- and 1,4- Cyclohexanedimethanol Cured with Diethylenetriamine:Sample 1 Onset of End of Residual Residual Exo- Peak Exo- Tg thermicityExotherm thermicity Enthalpy (° C.) (° C.) (° C.) (° C.) (J/g) 64.9151.9 175.9 239.0 5.6 65.5 157.0 179.3 224.8 4.7 (second scanning)

TABLE II Glass Transition Temperature for Diglycidyl Ether of cis-,trans-1,3- and 1,4- Cyclohexanedimethanol Cured with Diethylenetriamine:Sample 2 Onset of End of Residual Residual Tg Exo- Peak Exo- thermicityExotherm thermicity Enthalpy (° C.) (° C.) (° C.) (° C.) (J/g) 62.9155.8 180.6 241.4 3.6 62.4 none (second detected scanning)

Example 4 Moisture Resistance of Clear, Unfilled Casting ofThermosettable Blend of Re-Epoxidized Polyfunctional Oligomeric EpoxyResin and Diethylenetriamine

A pair of coupons were cut from the clear, unfilled casting of there-epoxidized PACE resin and DETA blend from Example 3, weighed, andeach added to a polypropylene bottle containing 100 mL of DI water. Onesample sealed in the polypropylene bottle was maintained at roomtemperature (23.5° C.) while the other was placed in an oven maintainedat 55° C. The samples were removed at the respective indicatedintervals, blotted with absorbent toweling, weighed and then replacedfor further testing. The results are given in Table III.

Comparative Example F Moisture Resistance of Clear, Unfilled Casting ofThermosettable Blend of Polyfunctional Oligomeric Epoxy Resin andDiethylenetriamine

A pair of coupons were cut from the clear, unfilled casting of the PACEresin and DETA blend from Comparative Example C, weighed, and each addedto a polypropylene bottle containing 100 mL of DI water and testedconcurrently using the method of Example 4. The results are given inTable III.

TABLE III Moisture Resistance Testing Weight Weight Cumu- IncreaseIncrease Sample lative in 23.5° C. in 55° C. Identification Time (hr) DIWater (%) DI Water (%) PACE resin 2.0 0.49 0.80 re-epoxidized PACE resin2.0 0.36 0.69 PACE resin 43.5 1.67 4.98 re-epoxidized PACE resin 43.51.42 3.87 PACE resin 67.25 1.87 5.60 re-epoxidized PACE resin 67.25 1.604.39 PACE resin 93.75 2.10 6.18 re-epoxidized PACE resin 93.75 1.74 4.83PACE resin 116.25 2.29 6.58 re-epoxidized PACE resin 116.25 1.88 5.19PACE resin 139.75 2.47 6.96 re-epoxidized PACE resin 139.75 2.00 5.52PACE resin 186.07 2.79 7.42 re-epoxidized PACE resin 186.07 2.21 6.03PACE resin 210.10 2.86 7.59 re-epoxidized PACE resin 210.10 2.30 6.26PACE resin 235.77 3.00 7.73 re-epoxidized PACE resin 235.77 2.39 6.45PACE resin 1177.2 5.33 not tested re-epoxidized PACE resin 1177.2 4.15not tested

What is claimed is:
 1. A re-epoxidized polyfunctional epoxy resincomposition comprising the reaction product of: (I) an epoxidizedpolyfunctional epoxy resin oligomeric composition comprising apolyfunctional aliphatic or cycloaliphatic epoxy resin which has beenisolated from an epoxy resin product formed as a result of anepoxidation process comprising the reaction of: (A) an aliphatic orcycloaliphatic hydroxyl-containing material; (B) an epihalohydrin, (C) abasic-acting substance, (D) a non-Lewis acid catalyst; and (E)optionally, one or more solvents; (II) an epihalohydrin; (III) a basicacting substance; (IV) a non-Lewis acid catalyst; and (V) optionally,one of more solvents.
 2. The composition of claim 1 wherein thealiphatic or cycloaliphatic hydroxyl containing material, component (A),comprises one or more of cyclohexanedialkanols, cyclohexenedialkanols,cyclohexanolmonoalkanols, cyclohexenolmonoalkanols,decahydronaphthalenedialkanols, octahydronaphthalenedialkanols;1,2,3,4-tetrahydronaphthalenedialkanols; or bridged cyclohexanols. 3.The composition of claim 2 wherein the cycloaliphatic hydroxylcontaining material, component (A), comprises a material selected fromthe group consisting of cycloaliphatic or polycycloaliphatic diols,monol monoalkanols or dialkanols including thedicyclopentadienedimethanols, the norbornenedimethanols, thenorbornanedimethanols, the cyclooctanedimethanols, thecyclooctenedimethanols, the cyclooctadienedimethanols, thepentacyclodecanedimethanols, the bicyclooctanedimethanols, thetricyclodecanedimethanols, the bicycloheptenedimethanols, thedicyclopentadienediols, the norbornenediols, the norbornanediols, thecyclooctanediols, the cyclooctenediols, the cyclooctadienediols, thecyclohexanediols, the cyclohexenediols, cyclopentane-1,3-diol;bicyclopentane-1,1′-diol; decahydronaphthalene-1,5-diol;trans,trans-2,6-dimethyl-2,6-octadiene-1,8-diol;5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane;3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane;3-methyl-2,2-norbornanedimethanol; 5-norbornene-2,3-dimethanol;norbornane-2,3-trans-dimethanol;perhydro-1,4:5,8-dimethanonaphthalene-2,3-trans-dimethanol;perhydro-1,4:5,8:9,10-trimethanoanthracene-2,3-trans-dimethanol; and5-norbornene-2,3-dimethanol; norbornanolmonomethanols; norbornenols; andmixtures thereof.
 4. The composition of claim 2 wherein the aliphatichydroxyl containing material, component (A), comprises a materialselected from the group consisting of alkoxylated phenolic reactantsincluding ethoxylated catechol, ethoxylated resorcinol, ethoxylatedhydroquinone, and ethoxylated bisphenol A; alkoxylation products of thehydrogenated aromatic phenolic reactants included ethoxylatedhydrogenated bisphenol A; neopentyl glycol, trimethylol propane,ethylene glycol, propylene glycol, triethylene glycol, higheralkoxylated ethylene glycols, pentaerythritol, 1,4-butanediol;1,6-hexanediol; and 1,12-dodecandiol; and mixtures thereof.
 5. Thecomposition of claim 2 wherein the aliphatic or cycloaliphatic hydroxylcontaining material, component (A), comprises one or more ofcyclohexanedialkanols or cyclohexenedialkanols.
 6. The composition ofclaim 2 wherein the aliphatic or cycloaliphatic hydroxyl containingmaterial, component (A), comprises cis-, trans-1,3- and1,4-cyclohexanedimethanol; cis-, trans-1,2-cyclohexanedimethanol; cis-,trans-1,3-cyclohexanedimethanol; cis-, trans-1,4-cyclohexanedimethanol;a methyl substituted cyclohexanedimethanol, including4-methyl-1,2-cyclohexanedimethanol or4-methyl-1,1-cyclohexanedimethanol; 1,1-cyclohexanedimethanol; acyclohexenedimethanol including 3-cyclohexene-1,1-dimethanol;3-cyclohexene-1,1-dimethanol, 6-methyl-;4,6-dimethyl-3-cyclohexene-1,1-dimethanol;cyclohex-2-ene-1,1-dimethanol; 1,1-cyclohexanediethanol;1,4-bis(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexanediethanol;1,4-(2-hydroxyethyloxy)cyclohexane; and1,4-(2-hydroxyethyloxy)cyclohex-2-ene.
 7. A process for preparing are-epoxidized polyfunctional epoxy resin composition comprisingreacting: (I) an epoxidized polyfunctional epoxy resin oligomericcomposition comprising a polyfunctional aliphatic or cycloaliphaticepoxy resin which has been isolated from an epoxy resin product formedas a result of an epoxidation process comprising the reaction of: (A) analiphatic or cycloaliphatic hydroxyl-containing material; (B) anepihalohydrin, (C) a basic-acting substance, (D) a non-Lewis acidcatalyst; and (E) optionally, one or more solvents; (II) anepihalohydrin; (III) a basic acting substance; (IV) a non-Lewis acidcatalyst; and; (V) optionally, one or more solvents.
 8. A curable epoxyresin composition comprising (a) a re-epoxidized polyfunctional epoxyresin composition of claim 1; (b) one or more curing agents; (c)optionally, one or more curing catalysts for curing epoxy resins; and(d) optionally, one or more epoxy resins other than the re-epoxidizedepoxy resin of component (a).
 9. The composition of claim 8, wherein thecuring material (b) comprises (a) di- and polyphenols, (b) di- andpolycarboxylic acids, (c) di- and polymercaptans, (d) di- andpolyamines, (e) primary monoamines, (f) sulfonamides, (g) aminophenols,(h) aminocarboxylic acids, (i) phenolic hydroxyl containing carboxylicacids, (j) sulfanilamides, and (k) mixtures thereof.
 10. The compositionof claim 8, including (d) one or more epoxy resins other than the epoxyresin of component (a); and wherein the one or more epoxy resins (d)comprises any epoxide containing compound which has an average of morethan one epoxide group per molecule.
 11. A partially (B-staged) curedthermoset product comprising the partially cured thermosettable epoxyresin composition of claim
 8. 12. A totally cured thermoset productcomprising the totally cured thermosettable epoxy resin composition ofclaim
 8. 13. A process for preparing the composition of claim 8comprising admixing: (a) a re-epoxidized polyfunctional epoxy resincomposition of claim 1; (b) one or more curing agents; (c) optionally,one or more curing catalysts for curing epoxy resins; and (d)optionally, one or more epoxy resins other than the re-epoxidized epoxyresin of component (A).
 14. A process for preparing the composition ofclaim 12 or claim 13 comprising the steps of: (I) admixing: (a) are-epoxidized polyfunctional epoxy resin composition of claim 1; (b) oneor more curing agents; (c) optionally, one or more curing catalysts forcuring epoxy resins; and (d) optionally, one or more epoxy resins otherthan the epoxy resin of component (A); and (II) carrying out theadmixing of step (I) at a temperature of from about 0° C. to about 300°C.
 15. An article made from the composition of claim
 8. 16. The articleof claim 15, wherein the article comprises a coating, a laminate, anencapsulation, a casting, a filament winding, a molding, a polymerconcrete, an adhesive bond, a paint, a lacquer, a varnish, or acomposite.